Etienne Cotter, Lucas Abounader, Ryan A. Shenvi. “A new twist on Hayashi–Miyaura arylation: overcoming the Fürst–Plattner torsional barrier.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007797/v1

(R)-2-Methyl-N-((4aS,8aR,E)-octahydronaphthalen-1(2H)-ylidene)propane-2-sulfinamide
Identifier S3
TLC Rf (Et₂O/pentane = 1:1) 0.50
¹H NMR (600 MHz, CDCl₃) δ 3.65 – 3.54 (m, 1H), 1.98 (td, J = 13.9, 12.7, 5.3 Hz, 2H), 1.94 – 1.84 (m, 2H), 1.76 (tdd, J = 16.2, 11.1, 3.5 Hz, 3H), 1.71 – 1.57 (m, 4H), 1.41 – 1.27 (m, 3H), 1.22 (s, 9H), 1.19 – 1.11 (m, 1H)
¹³C NMR (151 MHz, CDCl₃) δ 189.57, 56.57, 53.90, 45.70, 34.72, 34.54, 33.54, 29.85, 27.45, 27.19, 25.94, 22.39
HRMS Calculated for C₁₄H₂₆NOS [M + H]⁺: 256.1735 | Found: 256.1743
Optical rotation [α]ᴅ²⁵ = −34.0 (c = 0.5, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
Single-crystal X-ray diffraction, crystal data CCDC 2432515; identification code: Shenvi379; empirical formula: C₁₄H₂₅NOS; formula weight: 255.41; T = 100.00 K; λ = 0.71073 Å; monoclinic; space group P 1 21 1; a = 5.6694(5) Å, α = 90°; b = 23.775(2) Å, β = 94.109(3)°; c = 10.7894(8) Å, γ = 90°; V = 1450.5(2) ų; Z = 4; calculated density = 1.170 Mg/m³; absorption coefficient = 0.210 mm⁻¹; F(000) = 560
Single-crystal X-ray diffraction, data collection and refinement Crystal size: 0.18 × 0.03 × 0.03 mm³; θ = 3.192–26.441°; index ranges: −7 ≤ h ≤ 7, −29 ≤ k ≤ 29, −13 ≤ l ≤ 13; reflections collected: 68355; independent reflections: 5924 [R(int) = 0.0626]; completeness to θ = 25.242°: 99.7 %; semi-empirical absorption correction from equivalents; maximum and minimum transmission: 0.646471 and 0.537563; full-matrix least-squares on F²; data/restraints/parameters: 5924/1/314; goodness-of-fit on F²: 1.053; final R indices [I > 2sigma(I)]: R1 = 0.0337, wR2 = 0.0751; R indices (all data): R1 = 0.0393, wR2 = 0.0782; absolute structure parameter: −0.02(4); largest difference peak and hole: 0.221 and −0.220 e Å⁻³
Single-crystal X-ray diffraction, refinement qualifier Twinned crystal; final refinement using HKL 5 file format
Single-crystal X-ray diffraction, asymmetric unit Two molecules
SI, pp. S5–S6, S160–S161
(R)-2-Methyl-N-((4aR,8aS,E)-octahydronaphthalen-1(2H)-ylidene)propane-2-sulfinamide
Identifier S4
TLC Rf (Et₂O/pentane = 1:1) 0.35
¹H NMR (600 MHz, CDCl₃) δ 3.51 (dddd, J = 14.0, 4.2, 2.8, 1.5 Hz, 1H), 2.20 (td, J = 13.9, 5.5 Hz, 1H), 2.01 – 1.91 (m, 3H), 1.85 – 1.66 (m, 4H), 1.53 (qt, J = 13.5, 4.0 Hz, 1H), 1.30 (ddt, J = 18.4, 10.6, 5.2 Hz, 2H), 1.23 (s, 12H), 1.21 – 1.12 (m, 1H)
¹³C NMR (151 MHz, CDCl₃) δ 190.33, 56.16, 53.68, 45.68, 34.76, 33.35, 29.85, 27.27, 26.88, 25.98, 25.89, 22.32
HRMS Calculated for C₁₄H₂₆NOS [M + H]⁺: 256.1735 | Found: 256.1739
Optical rotation [α]ᴅ²⁵ = −200.0 (c = 0.5, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
Single-crystal X-ray diffraction, crystal data CCDC 2430655; identification code: shenvi374_b_0m_a; empirical formula: C₁₄H₂₅NOS; formula weight: 255.41; T = 100 K; λ = 0.71073 Å; orthorhombic; space group P212121; a = 5.578(3) Å, α = 90°; b = 10.685(10) Å, β = 90°; c = 23.420(12) Å, γ = 90°; V = 1395.8(17) ų; Z = 4; calculated density = 1.215 Mg/m³; absorption coefficient = 0.218 mm⁻¹; F(000) = 560
Single-crystal X-ray diffraction, data collection and refinement Crystal size: 0.21 × 0.07 × 0.03 mm³; θ = 2.581–26.808°; index ranges: −6 ≤ h ≤ 7, −13 ≤ k ≤ 13, −29 ≤ l ≤ 29; reflections collected: 22433; independent reflections: 2952 [R(int) = 0.0907]; completeness to θ = 25.242°: 99.8 %; semi-empirical absorption correction from equivalents; maximum and minimum transmission: 0.2506 and 0.1382; full-matrix least-squares on F²; data/restraints/parameters: 2952/0/157; goodness-of-fit on F²: 1.054; final R indices [I > 2sigma(I)]: R1 = 0.0450, wR2 = 0.1120; R indices (all data): R1 = 0.0518, wR2 = 0.1159; absolute structure parameter: −0.03(7); largest difference peak and hole: 0.708 and −0.279 e Å⁻³
Single-crystal X-ray diffraction, asymmetric unit One copy of the compound
SI, pp. S5, S7, S162–S163
(4S,8R)-trans-Decalone
Identifier S5
TLC Rf (Et₂O/pentane = 1:4) 0.6
¹H NMR (400 MHz, CDCl₃) δ 2.33 (qd, J = 13.6, 12.0, 6.3 Hz, 2H), 2.11 – 1.87 (m, 3H), 1.81 – 1.65 (m, 5H), 1.51 – 1.31 (m, 2H), 1.24 – 1.15 (m, 4H)
¹³C NMR (176 MHz, CDCl₃) δ 213.00, 55.23, 45.11, 41.98, 34.54, 33.20, 26.65, 25.90, 25.58, 25.25
HRMS Calculated for C₁₀H₁₇O [M + H]⁺: 153.1279 | Found: 153.1281
Optical rotation [α]ᴅ²⁵ = 2.5 (c = 1.0, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
Single-crystal X-ray diffraction, crystal data CCDC 2440437; identification code: shenvi383_a; empirical formula: C₁₀H₁₆O; formula weight: 152.23; T = 100.15 K; λ = 1.54178 Å; monoclinic; space group P 1 21 1; a = 7.2833(6) Å, α = 90°; b = 5.5468(5) Å, β = 103.639(4)°; c = 10.9112(10) Å, γ = 90°; V = 428.37(7) ų; Z = 2; calculated density = 1.180 Mg/m³; absorption coefficient = 0.567 mm⁻¹; F(000) = 168
Single-crystal X-ray diffraction, data collection and refinement Crystal size: 0.23 × 0.17 × 0.06 mm³; θ = 4.169–70.296°; index ranges: −8 ≤ h ≤ 8, −6 ≤ k ≤ 6, −13 ≤ l ≤ 12; reflections collected: 10524; independent reflections: 1603 [R(int) = 0.0497]; completeness to θ = 67.679°: 100.0 %; semi-empirical absorption correction from equivalents; maximum and minimum transmission: 0.5220 and 0.4281; full-matrix least-squares on F²; data/restraints/parameters: 1603/1/100; goodness-of-fit on F²: 1.100; final R indices [I > 2sigma(I)]: R1 = 0.0357, wR2 = 0.1039; R indices (all data): R1 = 0.0377, wR2 = 0.1057; absolute structure parameter: 0.09(13); largest difference peak and hole: 0.179 and −0.168 e Å⁻³
Single-crystal X-ray diffraction, asymmetric unit One copy of the compound
SI, pp. S8–S9, S164–S165
S6
Single-crystal X-ray diffraction, crystal data CCDC 2432562; identification code: shenvi380_0m_a; empirical formula: C₁₀H₁₆O; formula weight: 152.23; T = 100.15 K; λ = 1.54178 Å; monoclinic; space group P 1 21 1; a = 7.2852(4) Å, α = 90°; b = 5.5376(3) Å, β = 103.656(2)°; c = 10.8823(5) Å, γ = 90°; V = 426.61(4) ų; Z = 2; calculated density = 1.185 Mg/m³; absorption coefficient = 0.569 mm⁻¹; F(000) = 168
Single-crystal X-ray diffraction, data collection and refinement Crystal size: 0.23 × 0.06 × 0.04 mm³; θ = 4.181–70.708°; index ranges: −8 ≤ h ≤ 8, −6 ≤ k ≤ 6, −13 ≤ l ≤ 13; reflections collected: 10617; independent reflections: 1618 [R(int) = 0.0395]; completeness to θ = 67.679°: 100.0 %; semi-empirical absorption correction from equivalents; maximum and minimum transmission: 0.5224 and 0.3624; full-matrix least-squares on F²; data/restraints/parameters: 1618/1/100; goodness-of-fit on F²: 1.064; final R indices [I > 2sigma(I)]: R1 = 0.0349, wR2 = 0.0976; R indices (all data): R1 = 0.0356, wR2 = 0.0983; absolute structure parameter: −0.04(17); largest difference peak and hole: 0.222 and −0.170 e Å⁻³
Single-crystal X-ray diffraction, asymmetric unit One copy of the compound
SI, pp. S166–S167
(4S,8R)-trans-Decalenone
Identifier 3
TLC Rf (Et₂O/pentane = 1:4) 0.5
¹H NMR (600 MHz, CDCl₃) δ 6.91 (ddd, J = 10.0, 6.0, 2.1 Hz, 1H), 5.98 (ddd, J = 10.0, 3.1, 1.0 Hz, 1H), 2.38 – 2.30 (m, 1H), 2.25 (dtd, J = 11.9, 3.5, 1.7 Hz, 1H), 2.11 (ddt, J = 18.7, 10.7, 2.6 Hz, 1H), 2.01 – 1.93 (m, 1H), 1.88 – 1.70 (m, 4H), 1.34 – 1.17 (m, 3H), 1.13 (tdd, J = 13.1, 11.3, 3.7 Hz, 1H)
¹³C NMR (151 MHz, CDCl₃) δ 201.60, 148.97, 129.71, 51.20, 40.22, 33.87, 33.76, 25.81, 25.62, 25.53
HRMS Calculated for C₁₀H₁₅O [M + H]⁺: 151.1123 | Found: 151.1124
Optical rotation [α]ᴅ²⁵ = 83.7 (c = 1.0, CHCl₃)
Chiral SFC report and ¹H and ¹³C NMR spectra Image data were not transcribed
Single-crystal X-ray diffraction, crystal data CCDC 2442950; identification code: shenvi384_0m_a; empirical formula: C₁₀H₁₄O; formula weight: 150.21; T = 100 K; λ = 1.54178 Å; monoclinic; space group P 1 21 1; a = 11.3189(4) Å, α = 90°; b = 5.9794(2) Å, β = 108.2500(10)°; c = 13.2796(4) Å, γ = 90°; V = 853.56(5) ų; Z = 4; calculated density = 1.169 Mg/m³; absorption coefficient = 0.568 mm⁻¹; F(000) = 328
Single-crystal X-ray diffraction, data collection and refinement Crystal size: 0.2 × 0.18 × 0.18 mm³; θ = 3.504–70.212°; index ranges: −13 ≤ h ≤ 13, −7 ≤ k ≤ 7, −16 ≤ l ≤ 16; reflections collected: 50581; independent reflections: 3198 [R(int) = 0.0287]; completeness to θ = 67.679°: 98.7 %; semi-empirical absorption correction from equivalents; maximum and minimum transmission: 0.5220 and 0.4385; full-matrix least-squares on F²; data/restraints/parameters: 3198/1/199; goodness-of-fit on F²: 1.091; final R indices [I > 2sigma(I)]: R1 = 0.0315, wR2 = 0.0892; R indices (all data): R1 = 0.0317, wR2 = 0.0894; absolute structure parameter: 0.06(4); largest difference peak and hole: 0.198 and −0.142 e Å⁻³
SI, pp. S11–S13, S168–S169
epi-3
Single-crystal X-ray diffraction, crystal data CCDC 2442951; identification code: shenvi385_0m_a; empirical formula: C₁₀H₁₄O; formula weight: 150.21; T = 100.15 K; λ = 1.54178 Å; monoclinic; space group P 1 21 1; a = 11.4176(5) Å, α = 90°; b = 5.9577(3) Å, β = 109.348(2)°; c = 13.3509(5) Å, γ = 90°; V = 856.87(7) ų; Z = 4; calculated density = 1.164 Mg/m³; absorption coefficient = 0.566 mm⁻¹; F(000) = 328
Single-crystal X-ray diffraction, data collection and refinement Crystal size: 0.15 × 0.12 × 0.12 mm³; θ = 3.509–70.426°; index ranges: −13 ≤ h ≤ 13, −7 ≤ k ≤ 7, −15 ≤ l ≤ 16; reflections collected: 33467; independent reflections: 3250 [R(int) = 0.0478]; completeness to θ = 67.679°: 100.0 %; semi-empirical absorption correction from equivalents; maximum and minimum transmission: 0.5220 and 0.4321; full-matrix least-squares on F²; data/restraints/parameters: 3250/241/236; goodness-of-fit on F²: 1.050; final R indices [I > 2sigma(I)]: R1 = 0.0360, wR2 = 0.0862; R indices (all data): R1 = 0.0405, wR2 = 0.0898; absolute structure parameter: 0.04(12); largest difference peak and hole: 0.125 and −0.166 e Å⁻³
Single-crystal X-ray diffraction, structural result Two molecules in the asymmetric unit; one molecule is disordered, with approximately 10 % having the opposite stereochemistry
SI, pp. S170–S171
(3R,4aS,8aR)-3-(Furan-3-yl)octahydronaphthalen-1(2H)-one
Identifier 5
TLC Rf (Et₂O/pentane = 1:4) 0.6
¹H NMR (600 MHz, CDCl₃) δ 7.37 (d, J = 1.8 Hz, 1H), 7.23 (s, 1H), 6.30 (d, J = 1.8 Hz, 1H), 2.94 (tt, J = 12.6, 3.9 Hz, 1H), 2.61 (ddd, J = 13.2, 4.2, 2.1 Hz, 1H), 2.39 (t, J = 13.2 Hz, 1H), 2.06 – 1.91 (m, 3H), 1.87 – 1.78 (m, 2H), 1.73 (dq, J = 8.5, 2.7 Hz, 1H), 1.60 – 1.37 (m, 2H), 1.28 – 1.19 (m, 4H)
¹³C NMR (126 MHz, CDCl₃) δ 211.34, 143.28, 137.84, 128.94, 109.24, 54.55, 48.42, 43.41, 40.24, 35.22, 34.36, 25.89, 25.50, 25.15
HRMS Calculated for C₁₄H₁₉O₂ [M + H]⁺: 219.1385 | Found: 219.1387
Optical rotation [α]ᴅ²⁵ = 6.6 (c = 1.0, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
Single-crystal X-ray diffraction, crystal data CCDC 2448226; identification code: shenvi387_0m_a; empirical formula: C₁₄H₁₈O₂; formula weight: 218.28; T = 100.00 K; λ = 1.54178 Å; orthorhombic; space group P212121; a = 5.5481(4) Å, α = 90°; b = 10.0564(7) Å, β = 90°; c = 20.9106(14) Å, γ = 90°; V = 1166.68(14) ų; Z = 4; calculated density = 1.243 Mg/m³; absorption coefficient = 0.644 mm⁻¹; F(000) = 472
Single-crystal X-ray diffraction, data collection and refinement Crystal size: 0.17 × 0.15 × 0.12 mm³; θ = 4.228–70.071°; index ranges: −6 ≤ h ≤ 6, −11 ≤ k ≤ 12, −25 ≤ l ≤ 25; reflections collected: 32503; independent reflections: 2211 [R(int) = 0.0361]; completeness to θ = 67.679°: 100.0 %; semi-empirical absorption correction from equivalents; maximum and minimum transmission: 0.5220 and 0.3737; full-matrix least-squares on F²; data/restraints/parameters: 2211/0/145; goodness-of-fit on F²: 1.042; final R indices [I > 2sigma(I)]: R1 = 0.0269, wR2 = 0.0693; R indices (all data): R1 = 0.0276, wR2 = 0.0699; absolute structure parameter: −0.02(5); largest difference peak and hole: 0.172 and −0.172 e Å⁻³
Single-crystal X-ray diffraction, asymmetric unit One copy of the compound
SI, pp. S25–S26, S172–S173
(3S,4aS,8aR)-3-(Furan-3-yl)octahydronaphthalen-1(2H)-one
Identifier epi-5
TLC Rf (Et₂O/pentane = 1:4) 0.55
¹H NMR (600 MHz, CDCl₃) δ 7.35 (t, J = 1.7 Hz, 1H), 7.18 (q, J = 1.3 Hz, 1H), 6.23 (dd, J = 1.7, 0.9 Hz, 1H), 3.45 – 3.38 (m, 1H), 2.74 – 2.59 (m, 2H), 2.01 – 1.81 (m, 4H), 1.81 – 1.70 (m, 1H), 1.70 – 1.63 (m, 2H), 1.41 (qt, J = 11.3, 3.6 Hz, 1H), 1.23 – 1.06 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 212.17, 143.17, 139.87, 127.95, 109.93, 55.32, 45.21, 39.04, 38.35, 34.17, 33.22, 25.74, 25.54, 24.96
HRMS Calculated for C₁₄H₁₉O₂ [M + H]⁺: 219.1385 | Found: 219.1387
Optical rotation [α]ᴅ²⁵ = 52.6 (c = 0.65, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S28–S29
(3R,4aS,8aR)-3-(Thiophen-3-yl)octahydronaphthalen-1(2H)-one
Identifier 8
TLC Rf (EtOAc/hexanes = 1:10) 0.60
¹H NMR (400 MHz, CDCl₃) δ 7.29 (dd, J = 4.9, 3.0 Hz, 1H), 6.99 (dq, J = 2.9, 1.4 Hz, 2H), 3.12 (tt, J = 12.8, 3.9 Hz, 1H), 2.67 (ddd, J = 13.2, 4.1, 2.1 Hz, 1H), 2.48 (td, J = 13.2, 1.3 Hz, 1H), 2.08 (dq, J = 13.1, 2.6 Hz, 1H), 2.06 – 1.92 (m, 1H), 1.88 – 1.71 (m, 3H), 1.65 (q, J = 12.3 Hz, 1H), 1.57 – 1.41 (m, 1H), 1.31 – 1.18 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 211.52, 145.71, 126.48, 126.03, 119.25, 54.54, 48.89, 43.47, 40.72, 39.73, 34.36, 25.89, 25.49, 25.16
HRMS Calculated for C₁₄H₁₈OS [M + H]⁺: 235.1157 | Found: 235.1164
Optical rotation [α]ᴅ²⁵ = 21.000 (c = 0.2, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S31–S32
tert-Butyl 3-((2R,4aR,8aS)-4-oxodecahydronaphthalen-2-yl)-1H-pyrrole-1-carboxylate
Identifier 9
TLC Rf (EtOAc/hexanes = 1:10) 0.55
¹H NMR (600 MHz, CDCl₃) δ 7.20 – 7.12 (m, 1H), 6.99 (s, 1H), 6.11 (dt, J = 3.3, 1.6 Hz, 1H), 2.92 (tt, J = 12.6, 4.0 Hz, 1H), 2.62 (ddt, J = 13.2, 4.1, 1.7 Hz, 1H), 2.39 (td, J = 13.2, 1.4 Hz, 1H), 2.07 – 1.92 (m, 3H), 1.87 – 1.71 (m, 3H), 1.58 (d, J = 1.4 Hz, 9H), 1.57 – 1.51 (m, 2H), 1.47 (tdd, J = 11.2, 7.9, 3.0 Hz, 1H), 1.25 – 1.21 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 211.78, 148.98, 131.19, 120.51, 115.40, 110.97, 83.70, 54.53, 48.63, 43.45, 40.52, 36.81, 34.38, 28.14, 25.90, 25.51, 25.16
HRMS Calculated for C₁₉H₂₇NO₃ [M + H]⁺: 318.2069 | Found: 318.2074
Optical rotation [α]ᴅ²⁵ = 8.750 (c = 0.4, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S33–S34
epi-9
TLC Rf (EtOAc/hexanes = 1:10) 0.50
¹H NMR (600 MHz, CDCl₃) δ 7.15 (d, J = 2.9 Hz, 1H), 6.96 (s, 1H), 6.06 (dt, J = 3.2, 1.4 Hz, 1H), 3.42 (q, J = 4.2 Hz, 1H), 2.67 (d, J = 5.0 Hz, 2H), 1.99 – 1.90 (m, 4H), 1.86 (dd, J = 12.2, 4.7 Hz, 1H), 1.82 – 1.74 (m, 1H), 1.71 – 1.64 (m, 2H), 1.58 (s, 9H), 1.49 – 1.41 (m, 1H), 1.21 (dd, J = 57.2, 9.0 Hz, 5H)
¹³C NMR (151 MHz, CDCl₃) δ 212.26, 148.92, 130.23, 120.43, 117.26, 111.74, 83.63, 55.28, 45.21, 38.91, 38.59, 34.29, 34.26, 29.84, 28.14, 25.73, 25.59, 24.99
HRMS Calculated for C₁₉H₁₇NO₃ [M + H]⁺: 318.2069 | Found: 318.2063
Optical rotation [α]ᴅ²⁵ = 19.000 (c = 0.2, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S35–S36
(3R,4aS,8aR)-3-(Pyridin-4-yl)octahydronaphthalen-1(2H)-one
Identifier 6
TLC Rf (EtOAc/hexanes = 1:1) 0.20
¹H NMR (400 MHz, CDCl₃) δ 8.59 – 8.52 (m, 2H), 7.18 – 7.10 (m, 2H), 3.01 (tt, J = 12.6, 4.1 Hz, 1H), 2.62 – 2.41 (m, 2H), 2.10 – 1.92 (m, 3H), 1.88 – 1.80 (m, 2H), 1.78 – 1.61 (m, 2H), 1.54 (qt, J = 11.3, 3.2 Hz, 1H), 1.36 – 1.15 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 210.56, 153.16, 150.13, 122.12, 54.54, 47.86, 43.62, 43.59, 39.94, 34.29, 25.81, 25.40, 25.09
HRMS Calculated for C₁₅H₁₉NO [M + H]⁺: 230.1545 | Found: 230.1547
Optical rotation [α]ᴅ²⁵ = 20.615 (c = 0.7, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
Single-crystal X-ray diffraction, crystal data CCDC 2523557; identification code: Shenvi410; empirical formula: C₁₅H₁₉NO; formula weight: 229.31; T = 100.00 K; λ = 1.54178 Å; orthorhombic; space group P212121; a = 5.5161(2) Å, α = 90°; b = 10.3231(4) Å, β = 90°; c = 21.6124(9) Å, γ = 90°; V = 1230.68(8) ų; Z = 4; calculated density = 1.238 Mg/m³; absorption coefficient = 0.597 mm⁻¹; F(000) = 496
Single-crystal X-ray diffraction, data collection and refinement Crystal size: 0.14 × 0.12 × 0.02 mm³; θ = 4.091–70.124°; index ranges: −6 ≤ h ≤ 6, −11 ≤ k ≤ 12, −25 ≤ l ≤ 26; reflections collected: 19420; independent reflections: 2341 [R(int) = 0.0357]; completeness to θ = 67.679°: 99.8 %; semi-empirical absorption correction from equivalents; maximum and minimum transmission: 0.7533 and 0.5788; full-matrix least-squares on F²; data/restraints/parameters: 2341/0/155; goodness-of-fit on F²: 1.071; final R indices [I > 2sigma(I)]: R1 = 0.0279, wR2 = 0.0664; R indices (all data): R1 = 0.0295, wR2 = 0.0674; absolute structure parameter: −0.02(10); extinction coefficient: 0.0015(4); largest difference peak and hole: 0.189 and −0.144 e Å⁻³
Single-crystal X-ray diffraction, crystal size (narrative) 0.075 × 0.050 × 0.030 mm³
SI, pp. S37–S38, S176–S177
(3R,4aS,8aR)-3-(Pyridin-3-yl)octahydronaphthalen-1(2H)-one
Identifier 10
TLC Rf (EtOAc/hexanes = 1:1) 0.20
¹H and ¹³C NMR sample composition Containing traces of undesired diastereomer
¹H NMR (400 MHz, CDCl₃) δ 8.53 – 8.47 (m, 2H), 7.54 (dt, J = 7.9, 2.0 Hz, 1H), 7.30 – 7.22 (m, 1H), 3.05 (tdd, J = 12.3, 5.0, 3.4 Hz, 1H), 2.61 – 2.48 (m, 2H), 2.10 – 1.92 (m, 3H), 1.90 – 1.82 (m, 2H), 1.78 – 1.66 (m, 2H), 1.55 (d, J = 10.4 Hz, 1H), 1.30 – 1.25 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 210.81, 148.70, 148.38, 139.52, 134.05, 123.73, 54.52, 48.58, 43.68, 42.03, 40.59, 34.31, 25.84, 25.45, 25.13
HRMS Calculated for C₁₅H₁₉NO [M + H]⁺: 230.1545 | Found: 230.1542
Optical rotation [α]ᴅ²⁵ = 31.000 (c = 0.2, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S39–S40
(3R,4aS,8aR)-3-(Pyridin-2-yl)octahydronaphthalen-1(2H)-one
Identifier 11
TLC Rf (EtOAc/hexanes = 1:4) 0.30
¹H NMR (400 MHz, CDCl₃) δ 8.57 (d, J = 4.6 Hz, 1H), 7.62 (dd, J = 8.4, 6.7 Hz, 1H), 7.19 – 7.09 (m, 2H), 3.17 (tt, J = 12.5, 3.9 Hz, 1H), 2.84 (t, J = 13.3 Hz, 1H), 2.61 – 2.51 (m, 1H), 2.08 (t, J = 11.2 Hz, 1H), 1.98 (t, J = 8.2 Hz, 2H), 1.95 – 1.68 (m, 5H), 1.36 – 1.16 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 212.17, 162.73, 149.52, 137.01, 122.00, 121.94, 54.49, 47.16, 46.32, 43.68, 39.65, 34.36, 29.85, 25.91, 25.51, 25.20
HRMS Calculated for C₁₅H₁₉NO [M + H]⁺: 230.1545 | Found: 230.1550
Optical rotation [α]ᴅ²⁵ = 6.250 (c = 0.1, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S41–S42
(3R,4aS,8aR)-3-(Pyrimidin-5-yl)octahydronaphthalen-1(2H)-one
Identifier 12
TLC Rf (EtOAc/hexanes = 1:1) 0.20
¹H and ¹³C NMR sample composition Containing traces of undesired diastereomer
¹H NMR (400 MHz, CDCl₃) δ 9.12 (s, 1H), 8.63 (s, 2H), 3.06 (tt, J = 12.6, 4.1 Hz, 1H), 2.66 – 2.50 (m, 2H), 2.14 – 1.95 (m, 3H), 1.86 (s, 2H), 1.82 – 1.69 (m, 2H), 1.37 – 1.14 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 209.80, 157.62, 155.53, 137.02, 76.95, 74.76, 54.48, 47.94, 43.57, 40.05, 39.87, 34.23, 25.78, 25.37, 25.07
HRMS Calculated for C₁₄H₁₈N₂O [M + H]⁺: 231.1497 | Found: 231.1499
Optical rotation [α]ᴅ²⁵ = 15.000 (c = 0.2, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S43–S44
(3S,4aS,8aR)-3-(Furan-2-yl)octahydronaphthalen-1(2H)-one
Identifier 13
TLC Rf (EtOAc/hexanes = 1:10) 0.55
¹H NMR (600 MHz, CDCl₃) δ 7.32 (d, J = 2.0 Hz, 1H), 6.29 (t, J = 2.6 Hz, 1H), 6.00 (d, J = 3.2 Hz, 1H), 3.11 (tt, J = 12.8, 4.1 Hz, 1H), 2.69 (ddd, J = 13.4, 4.4, 2.0 Hz, 1H), 2.51 (t, J = 13.4 Hz, 1H), 2.12 (dq, J = 13.3, 2.9 Hz, 1H), 1.99 (td, J = 14.6, 13.0, 9.4 Hz, 2H), 1.92 – 1.70 (m, 3H), 1.64 (q, J = 12.5 Hz, 1H), 1.49 (qd, J = 11.4, 3.2 Hz, 1H), 1.24 (d, J = 15.8 Hz, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 210.99, 157.65, 141.35, 110.18, 103.75, 54.60, 46.13, 43.05, 38.33, 37.70, 34.30, 25.85, 25.47, 25.12
HRMS Calculated for C₁₄H₁₈O₂ [M + H]⁺: 219.1385 | Found: 219.1392
Optical rotation [α]ᴅ²⁵ = 3.333 (c = 0.1, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S45–S46
(3R,4aS,8aR)-3-(Thiophen-2-yl)octahydronaphthalen-1(2H)-one
Identifier 14
TLC Rf (EtOAc/hexanes = 1:10) 0.55
¹H NMR (600 MHz, CDCl₃) δ 7.17 (dd, J = 5.1, 1.2 Hz, 1H), 6.94 (dd, J = 5.1, 3.5 Hz, 1H), 6.83 (dt, J = 3.5, 1.1 Hz, 1H), 3.32 (ttd, J = 13.2, 5.0, 4.4, 2.8 Hz, 1H), 2.74 (ddd, J = 13.3, 4.2, 2.2 Hz, 1H), 2.54 (td, J = 13.2, 1.3 Hz, 1H), 2.16 (dtd, J = 13.2, 3.4, 2.2 Hz, 1H), 2.08 – 1.91 (m, 2H), 1.89 – 1.81 (m, 2H), 1.78 – 1.65 (m, 2H), 1.55 – 1.42 (m, 1H), 1.26 (s, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 210.78, 148.73, 126.86, 123.26, 122.63, 54.44, 49.87, 43.26, 42.04, 39.60, 34.25, 25.85, 25.45, 25.12
HRMS Calculated for C₁₄H₁₉OS [M + H]⁺: 235.1157 | Found: 235.1159
Optical rotation [α]ᴅ²⁵ = 17.500 (c = 0.1, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S47–S48
(3R,4aS,8aR)-3-(Benzofuran-3-yl)octahydronaphthalen-1(2H)-one
Identifier 16
TLC Rf (EtOAc/hexanes = 1:4) 0.6
¹H NMR (400 MHz, CDCl₃) δ 7.60 (ddd, J = 7.6, 1.5, 0.7 Hz, 1H), 7.48 (dt, J = 8.1, 1.0 Hz, 1H), 7.42 (d, J = 1.1 Hz, 1H), 7.35 – 7.20 (m, 2H), 3.31 – 3.18 (m, 1H), 2.80 (ddd, J = 13.3, 4.1, 2.1 Hz, 1H), 2.58 (td, J = 13.3, 1.2 Hz, 1H), 2.21 (dtd, J = 13.1, 3.3, 2.1 Hz, 1H), 2.13 – 1.97 (m, 2H), 1.90 – 1.82 (m, 1H), 1.83 – 1.67 (m, 2H), 1.61 (dd, J = 12.1, 8.9 Hz, 1H), 1.39 – 1.16 (m, 3H)
¹³C NMR (151 MHz, CDCl₃) δ 211.08, 155.69, 140.17, 126.89, 124.58, 123.97, 122.57, 119.96, 111.88, 54.76, 47.58, 43.56, 39.43, 34.92, 34.36, 25.88, 25.49, 25.19
HRMS Calculated for C₁₈H₂₀O₂ [M + H]⁺: 269.1542 | Found: 269.1541
Optical rotation [α]ᴅ²⁵ = 36.000 (c = 0.15, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S49–S50
epi-16
TLC Rf (EtOAc/hexanes = 1:4) 0.6
¹H NMR (400 MHz, CDCl₃) δ 7.54 (dt, J = 7.6, 0.9 Hz, 1H), 7.47 (dt, J = 8.1, 1.0 Hz, 1H), 7.36 (d, J = 1.4 Hz, 1H), 7.34 – 7.28 (m, 1H), 7.23 (dd, J = 7.4, 1.1 Hz, 1H), 3.77 (ddt, J = 6.3, 4.1, 2.2 Hz, 1H), 2.91 – 2.70 (m, 2H), 2.25 – 2.12 (m, 1H), 2.09 – 1.91 (m, 3H), 1.77 (q, J = 6.6, 5.0 Hz, 1H), 1.68 – 1.58 (m, 2H), 1.47 – 1.28 (m, 1H), 1.23 – 0.99 (m, 2H)
¹³C NMR (151 MHz, CDCl₃) δ 212.42, 155.29, 142.40, 140.04, 127.08, 124.46, 124.37, 123.04, 122.44, 122.37, 119.84, 119.69, 111.75, 111.68, 55.28, 45.13, 39.11, 36.55, 33.83, 32.61, 29.72, 25.52, 25.36, 24.88
HRMS Calculated for C₁₈H₂₀O₂ [M + H]⁺: 269.1542 | Found: 269.1552
Optical rotation [α]ᴅ²⁵ = 124.800 (c = 0.2, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S51–S52
(3R,4aS,8aR)-3-(Benzo[b]thiophen-3-yl)octahydronaphthalen-1(2H)-one
Identifier 17
TLC Rf (EtOAc/hexanes = 1:4) 0.6
¹H NMR (400 MHz, CDCl₃) δ 7.93 – 7.83 (m, 1H), 7.78 – 7.72 (m, 1H), 7.37 (pd, J = 7.1, 1.4 Hz, 2H), 7.15 (d, J = 0.9 Hz, 1H), 3.44 (tt, J = 12.5, 3.5 Hz, 1H), 2.79 (ddd, J = 13.2, 3.9, 2.2 Hz, 1H), 2.60 (td, J = 13.3, 1.3 Hz, 1H), 2.21 (dq, J = 13.1, 3.0 Hz, 1H), 2.15 – 1.97 (m, 2H), 1.92 – 1.71 (m, 4H), 1.69 – 1.56 (m, 1H), 1.33 – 1.21 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 211.32, 139.54, 137.95, 124.62, 124.18, 123.18, 121.70, 120.22, 54.86, 47.99, 43.71, 39.94, 38.04, 34.37, 25.91, 25.51, 25.23
HRMS Calculated for C₁₈H₂₀OS [M + H]⁺: 285.1313 | Found: 285.1320
Optical rotation [α]ᴅ²⁵ = 57.222 (c = 0.2, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S53–S54
tert-Butyl 3-((2R,4aR,8aS)-4-oxodecahydronaphthalen-2-yl)-1H-indole-1-carboxylate
Identifier 18
TLC Rf (EtOAc/hexanes = 1:10) 0.5
¹H NMR (600 MHz, CDCl₃) δ 8.12 (s, 1H), 7.55 (d, J = 7.8 Hz, 1H), 7.37 (s, 1H), 7.32 (t, J = 7.9 Hz, 1H), 7.23 (d, J = 7.4 Hz, 1H), 3.27 (t, J = 12.8 Hz, 1H), 2.77 (dt, J = 13.5, 2.4 Hz, 1H), 2.56 (t, J = 13.3 Hz, 1H), 2.24 – 2.16 (m, 1H), 2.07 (t, J = 11.7 Hz, 1H), 1.99 (d, J = 13.5 Hz, 1H), 1.87 (d, J = 11.5 Hz, 3H), 1.74 (q, J = 12.5, 11.9 Hz, 3H), 1.68 (s, 9H), 1.59 (q, J = 11.0, 9.9 Hz, 1H), 1.25 (d, J = 32.2 Hz, 3H)
¹³C NMR (151 MHz, CDCl₃) δ 211.42, 124.66, 124.37, 122.58, 121.20, 119.20, 115.61, 54.80, 47.88, 43.66, 39.79, 35.58, 34.39, 29.86, 28.38, 25.91, 25.53, 25.22
HRMS Calculated for C₁₈H₂₀O₂ [M − Boc + 2H]⁺: 268.1701 | Found: 268.1707
Optical rotation [α]ᴅ²⁵ = 11.000 (c = 0.1, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S55–S56
epi-18
TLC Rf (EtOAc/hexanes = 1:10) 0.5
¹H NMR (600 MHz, CDCl₃) δ 8.15 (s, 1H), 7.52 (dd, J = 7.8, 1.1 Hz, 1H), 7.36 – 7.29 (m, 2H), 7.25 – 7.21 (m, 1H), 3.78 (dt, J = 6.8, 4.0 Hz, 1H), 2.88 – 2.71 (m, 2H), 2.14 (dq, J = 13.5, 2.8 Hz, 1H), 2.10 – 1.86 (m, 3H), 1.80 – 1.75 (m, 1H), 1.66 (s, 9H), 1.65 – 1.57 (m, 2H), 1.47 – 1.37 (m, 1H), 1.30 – 1.04 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 212.36, 149.64, 135.57, 129.61, 124.41, 123.44, 122.33, 119.07, 115.39, 83.56, 55.17, 45.14, 38.86, 36.79, 33.89, 32.92, 28.22, 25.53, 25.42, 24.92
HRMS Calculated for C₁₈H₂₀O₂ [M − Boc + 2H]⁺: 268.1701 | Found: 268.1700
Optical rotation [α]ᴅ²⁵ = 94.250 (c = 0.4, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S57–S58
tert-Butyl 4-((2R,4aR,8aS)-4-oxodecahydronaphthalen-2-yl)-3,6-dihydropyridine-1(2H)-carboxylate
Identifier 19
TLC Rf (EtOAc/hexanes = 1:4) 0.3
¹H NMR (500 MHz, CDCl₃) δ 5.38 (s, 1H), 3.88 – 3.84 (m, 2H), 3.47 (d, J = 5.9 Hz, 2H), 2.43 – 2.18 (m, 3H), 2.05 (d, J = 9.8 Hz, 2H), 1.92 (t, J = 9.0 Hz, 2H), 1.81 (td, J = 8.9, 8.0, 4.3 Hz, 3H), 1.71 (d, J = 5.9 Hz, 1H), 1.46 (s, 9H), 1.45 – 1.33 (m, 2H), 1.26 – 1.15 (m, 4H)
¹³C NMR (126 MHz, CDCl₃) δ 212.06, 79.72, 54.61, 46.33, 45.20, 43.42, 38.10, 34.43, 28.61, 25.89, 25.47, 25.16
HRMS Calculated for C₂₀H₃₁NO₃ [M + Na]⁺: 356.2202 | Found: 356.2197
Optical rotation [α]ᴅ²⁵ = 7.750 (c = 0.4, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S59–S60
(3R,4aS,8aR)-3-Phenyloctahydronaphthalen-1(2H)-one
Identifier 4
TLC Rf (Et₂O/pentane = 1:4) 0.75
¹H NMR (700 MHz, CDCl₃) δ 7.32 (t, J = 7.5 Hz, 2H), 7.23 (t, J = 8.3 Hz, 3H), 3.02 (tt, J = 12.6, 4.1 Hz, 1H), 2.62 – 2.49 (m, 2H), 2.05 (td, J = 11.4, 3.2 Hz, 1H), 1.98 (tq, J = 10.2, 3.1 Hz, 2H), 1.83 (dt, J = 9.8, 3.6 Hz, 2H), 1.74 (td, J = 4.7, 2.3 Hz, 1H), 1.72 – 1.68 (m, 1H), 1.52 (qt, J = 11.4, 3.4 Hz, 1H), 1.32 – 1.24 (m, 4H)
¹³C NMR (176 MHz, CDCl₃) δ 211.76, 144.48, 128.81, 126.79, 126.64, 54.57, 49.13, 44.54, 43.80, 41.04, 34.41, 25.92, 25.53, 25.20
HRMS Calculated for C₁₆H₂₀O [M + H]⁺: 229.1592 | Found: 229.1596
Optical rotation [α]ᴅ²⁵ = 54.600 (c = 0.5, CHCl₃)
Single-crystal X-ray diffraction, crystal data CCDC 2469776; identification code: shenvi395_0m_a; empirical formula: C₁₆H₂₀O; formula weight: 228.32; T = 100.00 K; λ = 1.54178 Å; orthorhombic; space group P212121; a = 5.5625(2) Å, α = 90°; b = 10.3893(3) Å, β = 90°; c = 21.8797(7) Å, γ = 90°; V = 1264.44(7) ų; Z = 4; calculated density = 1.199 Mg/m³; absorption coefficient = 0.555 mm⁻¹; F(000) = 496
Single-crystal X-ray diffraction, data collection and refinement Crystal size: 0.17 × 0.05 × 0.03 mm³; θ = 4.041–70.085°; index ranges: −6 ≤ h ≤ 6, −10 ≤ k ≤ 12, −26 ≤ l ≤ 25; reflections collected: 18018; independent reflections: 2388 [R(int) = 0.0440]; completeness to θ = 67.679°: 99.5 %; semi-empirical absorption correction from equivalents; maximum and minimum transmission: 0.5220 and 0.4027; full-matrix least-squares on F²; data/restraints/parameters: 2388/0/154; goodness-of-fit on F²: 1.064; final R indices [I > 2sigma(I)]: R1 = 0.0315, wR2 = 0.0761; R indices (all data): R1 = 0.0339, wR2 = 0.0774; absolute structure parameter: −0.05(15); largest difference peak and hole: 0.115 and −0.161 e Å⁻³
Single-crystal X-ray diffraction, asymmetric unit One copy of the compound
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S61–S62, S174–S175
(3S,4aS,8aR)-3-Phenyloctahydronaphthalen-1(2H)-one
Identifier epi-4
TLC Rf (Et₂O/pentane = 1:4) 0.80
¹H NMR (700 MHz, CDCl₃) δ 7.29 (t, J = 7.5 Hz, 2H), 7.19 (t, J = 6.9 Hz, 3H), 3.61 (dq, J = 7.1, 3.1 Hz, 1H), 2.86 – 2.68 (m, 2H), 2.06 – 1.92 (m, 3H), 1.80 – 1.76 (m, 1H), 1.63 (td, J = 9.4, 9.0, 5.1 Hz, 1H), 1.36 (qt, J = 11.5, 3.7 Hz, 1H), 1.24 – 1.08 (m, 3H)
¹³C NMR (176 MHz, CDCl₃) δ 213.00, 144.96, 128.51, 127.62, 126.21, 55.14, 44.68, 40.36, 39.97, 37.69, 34.27, 25.66, 25.62, 25.11
HRMS Calculated for C₁₆H₂₀O [M + H]⁺: 229.1592 | Found: 229.1595
Optical rotation [α]ᴅ²⁵ = 120.600 (c = 0.5, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S63–S64
(3R,4aS,8aR)-3-(p-Tolyl)octahydronaphthalen-1(2H)-one
Identifier 20
TLC Rf (EtOAc/hexanes = 1:10) 0.65
¹H NMR (600 MHz, CDCl₃) δ 7.12 (q, J = 8.2 Hz, 4H), 3.03 – 2.94 (m, 1H), 2.60 – 2.48 (m, 2H), 2.33 (s, 3H), 2.06 – 2.01 (m, 1H), 1.96 (dtd, J = 13.2, 3.5, 2.0 Hz, 2H), 1.83 (ddd, J = 11.3, 4.9, 3.0 Hz, 2H), 1.74 (dt, J = 8.1, 2.7 Hz, 1H), 1.69 (q, J = 12.4 Hz, 1H), 1.51 (qt, J = 11.4, 3.4 Hz, 1H), 1.30 – 1.21 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 211.83, 141.44, 136.23, 129.34, 126.38, 54.42, 49.15, 44.03, 43.66, 41.02, 34.28, 25.79, 25.40, 25.08, 21.01
HRMS Calculated for C₁₇H₂₃O [M + H]⁺: 243.1749 | Found: 243.1753
Optical rotation [α]ᴅ²⁵ = 29.143 (c = 0.35, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S65–S66
(3R,4aS,8aR)-3-(m-Tolyl)octahydronaphthalen-1(2H)-one
Identifier 21
TLC Rf (EtOAc/hexanes = 1:10) 0.65
¹H NMR (600 MHz, CDCl₃) δ 7.21 (t, J = 7.5 Hz, 1H), 7.07 – 6.99 (m, 3H), 2.98 (tdd, J = 12.3, 5.4, 3.5 Hz, 1H), 2.61 – 2.50 (m, 2H), 2.35 (s, 3H), 2.04 (td, J = 11.2, 3.3 Hz, 1H), 1.97 (dtd, J = 13.2, 3.5, 1.6 Hz, 2H), 1.86 – 1.80 (m, 2H), 1.78 – 1.63 (m, 2H), 1.51 (qt, J = 11.2, 3.2 Hz, 1H), 1.34 – 1.17 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 211.92, 144.47, 138.41, 128.70, 127.53, 127.45, 123.65, 54.57, 49.17, 44.50, 43.82, 41.06, 34.41, 25.92, 25.53, 25.20, 21.63
HRMS Calculated for C₁₇H₂₃O [M + H]⁺: 243.1749 | Found: 243.1756
Optical rotation [α]ᴅ²⁵ = 47.500 (c = 0.2, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S67–S68
(3R,4aS,8aR)-3-(o-Tolyl)octahydronaphthalen-1(2H)-one
Identifier 22
TLC Rf (EtOAc/hexanes = 1:10) 0.65
¹H NMR (400 MHz, CDCl₃) δ 7.25 – 7.09 (m, 4H), 3.24 (tq, J = 12.4, 3.7 Hz, 1H), 2.60 – 2.44 (m, 2H), 2.31 (s, 3H), 2.07 (td, J = 11.4, 3.2 Hz, 1H), 2.02 – 1.95 (m, 1H), 1.93 – 1.87 (m, 1H), 1.84 (q, J = 5.2 Hz, 2H), 1.78 – 1.64 (m, 2H), 1.58 – 1.48 (m, 0H), 1.28 – 1.22 (m, 5H)
¹³C NMR (151 MHz, CDCl₃) δ 211.98, 142.36, 135.24, 130.77, 126.56, 126.47, 125.11, 54.76, 48.37, 44.05, 40.35, 39.96, 34.41, 25.93, 25.54, 25.24, 19.43
HRMS Calculated for C₁₇H₂₃O [M + H]⁺: 243.1749 | Found: 243.1757
Optical rotation [α]ᴅ²⁵ = 50.500 (c = 0.2, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S69–S70
(3R,4aS,8aR)-3-(4-(Trifluoromethyl)phenyl)octahydronaphthalen-1(2H)-one
Identifier 23
TLC Rf (EtOAc/hexanes = 1:10) 0.50
¹H NMR (400 MHz, CDCl₃) δ 7.58 (d, J = 8.1 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 3.08 (tdd, J = 12.2, 5.3, 3.6 Hz, 1H), 2.63 – 2.48 (m, 2H), 2.12 – 1.93 (m, 3H), 1.90 – 1.79 (m, 2H), 1.79 – 1.65 (m, 2H), 1.61 – 1.48 (m, 2H), 1.31 – 1.20 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 210.98, 148.30, 129.26, 129.04, 127.06, 125.85, 125.82, 125.79, 125.77, 54.56, 48.71, 44.29, 43.68, 40.67, 34.34, 25.85, 25.46, 25.15
¹⁹F NMR (565 MHz, CDCl₃) δ −62.43
HRMS Calculated for C₁₇H₂₀F₃O [M + H]⁺: 297.1466 | Found: 297.1474
Optical rotation [α]ᴅ²⁵ = 24.200 (c = 0.5, CHCl₃)
¹H, ¹³C, and ¹⁹F NMR spectra Image data were not transcribed
SI, pp. S71–S73
(3R,4aS,8aR)-3-(3-(Trifluoromethyl)phenyl)octahydronaphthalen-1(2H)-one
Identifier 24
TLC Rf (EtOAc/hexanes = 1:10) 0.50
¹H NMR (400 MHz, CDCl₃) δ 7.53 – 7.36 (m, 4H), 3.15 – 3.02 (m, 1H), 2.63 – 2.49 (m, 2H), 2.12 – 1.94 (m, 3H), 1.84 (dd, J = 9.7, 3.7 Hz, 2H), 1.79 – 1.66 (m, 2H), 1.51 (d, J = 14.8 Hz, 1H), 1.25 (d, J = 6.8 Hz, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 210.97, 145.28, 131.25, 131.04, 130.22, 129.31, 123.74, 123.72, 123.35, 54.54, 48.83, 44.25, 43.66, 40.72, 34.34, 29.85, 25.87, 25.46, 25.14
¹⁹F NMR (565 MHz, CDCl₃) δ −62.57
HRMS Calculated for C₁₇H₂₀F₃O [M + H]⁺: 297.1466 | Found: 297.1471
Optical rotation [α]ᴅ²⁵ = 24.000 (c = 0.3, CHCl₃)
¹H, ¹³C, and ¹⁹F NMR spectra Image data were not transcribed
SI, pp. S74–S76
(3R,4aS,8aR)-3-(3,5-Bis(trifluoromethyl)phenyl)octahydronaphthalen-1(2H)-one
Identifier 25
TLC Rf (EtOAc/hexanes = 1:10) 0.60
¹H NMR (600 MHz, CDCl₃) δ 7.76 (s, 1H), 7.66 (d, J = 1.7 Hz, 2H), 3.17 (tt, J = 12.8, 3.9 Hz, 1H), 2.65 – 2.49 (m, 2H), 2.11 – 1.95 (m, 4H), 1.95 – 1.68 (m, 5H), 1.54 (dd, J = 11.4, 8.1 Hz, 1H), 1.33 – 1.20 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 210.02, 146.70, 132.47, 132.25, 132.03, 131.81, 126.99, 124.32, 122.51, 121.00, 120.97, 120.94, 77.37, 77.16, 76.95, 54.51, 48.49, 44.04, 43.52, 40.44, 34.26, 25.81, 25.40, 25.09
¹⁹F NMR (565 MHz, CDCl₃) δ −62.83
HRMS Calculated for C₁₈H₁₉F₆O [M + H]⁺: 364.1340 | Found: 364.1343
Optical rotation [α]ᴅ²⁵ = 18.400 (c = 0.5, CHCl₃)
¹H, ¹³C, and ¹⁹F NMR spectra Image data were not transcribed
SI, pp. S77–S79
(3R,4aS,8aR)-3-(3,4,5-Trifluorophenyl)octahydronaphthalen-1(2H)-one
Identifier 26
TLC Rf (EtOAc/hexanes = 1:10) 0.45
¹H NMR (600 MHz, CDCl₃) δ 6.87 – 6.79 (m, 2H), 2.95 (tt, J = 12.8, 3.8 Hz, 1H), 2.54 (ddd, J = 13.2, 4.2, 2.2 Hz, 1H), 2.43 (td, J = 13.3, 1.3 Hz, 1H), 2.08 – 1.91 (m, 3H), 1.84 (t, J = 6.4 Hz, 2H), 1.81 – 1.71 (m, 1H), 1.62 (q, J = 12.4 Hz, 1H), 1.50 (dtd, J = 11.4, 9.5, 8.0, 3.2 Hz, 1H), 1.27 – 1.19 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 210.38, 152.28, 152.26, 152.21, 152.19, 150.62, 150.56, 150.53, 140.63, 140.59, 139.36, 139.26, 137.80, 137.70, 137.60, 110.73, 110.70, 110.62, 110.59, 54.47, 48.65, 43.61, 43.36, 40.56, 34.28, 25.81, 25.40, 25.09
¹⁹F NMR (565 MHz, CDCl₃) δ −133.95, −133.96, −133.97, −133.97, −133.98, −134.00, −162.96, −162.98, −162.99, −163.01, −163.03
HRMS Calculated for C₁₆H₁₈F₃O [M + H]⁺: 283.1310 | Found: 283.1314
Optical rotation [α]ᴅ²⁵ = 30.000 (c = 0.4, CHCl₃)
¹H, ¹³C, and ¹⁹F NMR spectra Image data were not transcribed
SI, pp. S80–S82
(3R,4aS,8aR)-3-(3,5-Difluorophenyl)octahydronaphthalen-1(2H)-one
Identifier 27
TLC Rf (EtOAc/hexanes = 1:10) 0.55
¹H NMR (600 MHz, CDCl₃) δ 6.87 – 6.79 (m, 2H), 2.95 (tt, J = 12.8, 3.8 Hz, 1H), 2.54 (ddd, J = 13.2, 4.2, 2.2 Hz, 1H), 2.43 (td, J = 13.3, 1.3 Hz, 1H), 2.08 – 1.91 (m, 3H), 1.84 (t, J = 6.4 Hz, 2H), 1.81 – 1.71 (m, 1H), 1.62 (q, J = 12.4 Hz, 1H), 1.50 (dtd, J = 11.4, 9.5, 8.0, 3.2 Hz, 1H), 1.27 – 1.19 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 210.67, 164.19, 164.10, 162.54, 162.46, 148.36, 148.31, 148.25, 109.67, 109.63, 109.54, 109.50, 102.41, 102.24, 102.07, 54.52, 48.56, 44.06, 43.47, 40.51, 34.30, 25.84, 25.43, 25.11
¹⁹F NMR (565 MHz, CDCl₃) δ −109.55, −109.57, −109.58
HRMS Calculated for C₁₆H₁₉F₂O [M + H]⁺: 265.1404 | Found: 265.1406
Optical rotation [α]ᴅ²⁵ = 30.667 (c = 0.4, CHCl₃)
¹H, ¹³C, and ¹⁹F NMR spectra Image data were not transcribed
SI, pp. S83–S85
(3R,4aS,8aR)-3-(2-Fluorophenyl)octahydronaphthalen-1(2H)-one
Identifier 28
TLC Rf (EtOAc/hexanes = 1:10) 0.50
¹H NMR (600 MHz, CDCl₃) δ 7.24 – 7.18 (m, 2H), 7.10 (dd, J = 7.5, 1.3 Hz, 1H), 7.02 (ddd, J = 10.7, 8.1, 1.3 Hz, 1H), 3.32 (tt, J = 12.8, 4.0 Hz, 1H), 2.67 – 2.49 (m, 2H), 2.10 – 1.91 (m, 3H), 1.87 – 1.70 (m, 4H), 1.57 – 1.54 (m, 1H), 1.35 – 1.16 (m, 3H)
¹³C NMR (151 MHz, CDCl₃) δ 211.32, 161.49, 159.86, 131.10, 131.00, 128.25, 128.19, 127.67, 127.63, 124.47, 124.44, 115.91, 115.76, 54.64, 47.30, 43.65, 39.51, 37.92, 34.33, 25.88, 25.52, 25.18
¹⁹F NMR (565 MHz, CDCl₃) δ −118.52, −118.53, −118.54, −118.55, −118.56
HRMS Calculated for C₁₆H₂₀FO [M + H]⁺: 247.1498 | Found: 247.1505
Optical rotation [α]ᴅ²⁵ = 32.800 (c = 0.25, CHCl₃)
¹H, ¹³C, and ¹⁹F NMR spectra Image data were not transcribed
SI, pp. S86–S88
(3R,4aS,8aR)-3-(4-Chlorophenyl)octahydronaphthalen-1(2H)-one
Identifier 29
TLC Rf (EtOAc/hexanes = 1:10) 0.50
¹H NMR (400 MHz, CDCl₃) δ 7.31 – 7.27 (m, 2H), 7.18 – 7.11 (m, 2H), 2.99 (tt, J = 12.5, 4.1 Hz, 1H), 2.60 – 2.43 (m, 2H), 2.08 – 1.91 (m, 3H), 1.91 – 1.72 (m, 3H), 1.67 (dt, J = 13.2, 12.0 Hz, 1H), 1.57 (s, 2H), 1.29 – 1.20 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 211.30, 142.89, 132.44, 128.93, 128.02, 54.53, 49.02, 43.90, 43.67, 40.89, 34.36, 25.87, 25.48, 25.15
HRMS Calculated for C₁₆H₂₀ClO [M + H]⁺: 263.1203 | Found: 263.1209
Optical rotation [α]ᴅ²⁵ = 28.000 (c = 0.25, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S89–S90
(3R,4aS,8aR)-3-(4-Nitrophenyl)octahydronaphthalen-1(2H)-one
Identifier 30
TLC Rf (EtOAc/hexanes = 1:10) 0.65
¹H NMR (600 MHz, CDCl₃) δ 8.23 – 8.17 (m, 2H), 7.40 – 7.37 (m, 2H), 3.14 (tt, J = 12.7, 4.0 Hz, 1H), 2.62 – 2.50 (m, 2H), 2.22 (td, J = 7.7, 3.0 Hz, 1H), 2.07 (td, J = 11.3, 3.2 Hz, 1H), 2.00 (ddt, J = 13.5, 7.6, 3.6 Hz, 3H), 1.88 – 1.82 (m, 2H), 1.80 – 1.70 (m, 2H), 1.63 (q, J = 7.3 Hz, 1H), 1.35 – 1.23 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 210.39, 151.67, 146.93, 127.61, 124.25, 124.21, 54.58, 48.44, 44.30, 43.64, 40.45, 34.32, 25.82, 25.42, 25.11
HRMS Calculated for C₁₆H₂₀NO₃ [M + H]⁺: 274.1443 | Found: 274.1443
Optical rotation [α]ᴅ²⁵ = 11.111 (c = 0.1, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S91–S92
(3S,4aS,8aR)-3-(4-Nitrophenyl)octahydronaphthalen-1(2H)-one
Identifier epi-30
TLC Rf (EtOAc/hexanes = 1:10) 0.65
¹H NMR (600 MHz, CDCl₃) δ 8.17 – 8.12 (m, 2H), 7.36 (d, J = 8.3 Hz, 2H), 3.71 (tt, J = 6.0, 3.0 Hz, 1H), 2.88 – 2.67 (m, 2H), 2.10 – 1.94 (m, 4H), 1.85 – 1.75 (m, 1H), 1.73 – 1.59 (m, 2H), 1.35 – 1.04 (m, 6H)
¹³C NMR (151 MHz, CDCl₃) δ 212.08, 128.52, 123.81, 55.15, 44.25, 40.55, 39.63, 38.02, 34.12, 25.56, 25.42, 24.99
HRMS Calculated for C₁₆H₂₀NO₃ [M + H]⁺: 274.1443 | Found: 274.1443
Optical rotation [α]ᴅ²⁵ = 24.100 (c = 0.4, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S93–S94
Ethyl 4-((2R,4aR,8aS)-4-oxodecahydronaphthalen-2-yl)benzoate
Identifier 31
TLC Rf (EtOAc/hexanes = 1:10) 0.35
¹H NMR (600 MHz, CDCl₃) δ 8.00 (d, J = 7.9 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 4.37 (q, J = 7.0 Hz, 2H), 3.13 – 3.02 (m, 1H), 2.66 – 2.46 (m, 2H), 2.05 (td, J = 11.2, 3.3 Hz, 1H), 2.01 – 1.94 (m, 2H), 1.84 (q, J = 5.6, 4.8 Hz, 2H), 1.78 – 1.68 (m, 2H), 1.53 (qd, J = 9.7, 8.0, 5.5 Hz, 1H), 1.39 (t, J = 7.1 Hz, 3H), 1.28 – 1.22 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 211.20, 166.56, 149.43, 130.16, 129.12, 126.68, 61.06, 54.57, 48.71, 44.49, 43.74, 40.62, 34.35, 25.87, 25.47, 25.15, 14.49
HRMS Calculated for C₁₉H₂₅O₃ [M + H]⁺: 301.1804 | Found: 301.1808
Optical rotation [α]ᴅ²⁵ = 37.000 (c = 0.3, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S95–S96
(3R,4aS,8aR)-3-(4-(Methylthio)phenyl)octahydronaphthalen-1(2H)-one
Identifier 32
TLC Rf (Et₂O/pentane = 1:4) 0.60
¹H NMR (400 MHz, CDCl₃) δ 7.24 – 7.21 (m, 2H), 7.16 – 7.12 (m, 2H), 2.97 (ddt, J = 16.3, 8.4, 4.2 Hz, 1H), 2.59 – 2.49 (m, 2H), 2.47 (s, 3H), 2.07 – 1.91 (m, 2H), 1.87 – 1.80 (m, 2H), 1.77 – 1.61 (m, 2H), 1.53 – 1.45 (m, 0H), 1.28 – 1.20 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 211.65, 141.52, 136.57, 127.27, 127.18, 54.54, 49.12, 44.03, 43.73, 40.98, 34.39, 25.90, 25.51, 25.18, 16.24
HRMS Calculated for C₁₇H₂₃OS [M + H]⁺: 275.1470 | Found: 275.1472
Optical rotation [α]ᴅ²⁵ = 17.250 (c = 0.4, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S97–S98
tert-Butyl (3-((2R,4aR,8aS)-4-oxodecahydronaphthalen-2-yl)phenyl)carbamate
Identifier 33
TLC Rf (acetone/hexanes = 1:4) 0.40
¹H and ¹³C NMR sample composition Unknown impurities in the 0.8–1.4 ppm region in the ¹H NMR region and 0–40 ppm in ¹³C NMR, even after several consecutive PTLCs
¹H NMR (400 MHz, CDCl₃) δ 7.37 (s, 1H), 7.23 (t, J = 7.8 Hz, 1H), 7.14 – 7.03 (m, 1H), 6.88 (d, J = 7.8 Hz, 1H), 6.46 (s, 1H), 3.05 – 2.93 (m, 1H), 2.60 – 2.52 (m, 2H), 2.08 – 1.95 (m, 1H), 1.82 (d, J = 9.1 Hz, 2H), 1.71 (q, J = 12.3 Hz, 2H), 1.52 (s, 9H), 1.34 – 1.10 (m, 13H)
¹³C NMR (151 MHz, CDCl₃) δ 210.56, 151.68, 144.43, 137.63, 128.19, 120.21, 115.74, 115.57, 53.38, 47.83, 43.45, 42.62, 39.77, 33.20, 28.69, 27.34, 24.75, 24.36, 24.03
HRMS Calculated for C₂₁H₃₀NNaO₃ [M + Na]⁺: 366.2045 | Found: 366.2053
Optical rotation [α]ᴅ²⁵ = 41.875 (c = 0.16, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S99–S100
tert-Butyl (4-((2R,4aR,8aS)-4-oxodecahydronaphthalen-2-yl)phenyl)carbamate
Identifier 34
TLC Rf (acetone/hexanes = 1:4) 0.40
¹H and ¹³C NMR sample composition Unknown impurities in the 0.8–1.4 ppm region in the ¹H NMR region and 0–40 ppm in ¹³C NMR, even after several consecutive PTLCs
¹H NMR (600 MHz, CDCl₃) δ 7.23 (d, J = 8.0 Hz, 2H), 7.09 – 7.04 (m, 2H), 6.36 (s, 1H), 2.90 (tt, J = 12.6, 4.0 Hz, 1H), 2.51 – 2.39 (m, 2H), 2.00 – 1.80 (m, 5H), 1.76 (dt, J = 11.7, 4.0 Hz, 2H), 1.71 – 1.53 (m, 2H), 1.44 (d, J = 3.2 Hz, 10H), 1.19 (d, J = 5.7 Hz, 11H)
¹³C NMR (151 MHz, CDCl₃) δ 210.64, 151.77, 138.08, 135.74, 126.96, 125.95, 117.85, 53.34, 48.10, 42.74, 42.55, 39.87, 33.21, 28.66, 27.29, 24.72, 24.33, 24.00, −0.02
HRMS Calculated for C₂₁H₃₀NNaO₃ [M + Na]⁺: 366.2045 | Found: 366.2045
Optical rotation [α]ᴅ²⁵ = 6.000 (c = 0.1, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S101–S102
(3R,4aS,8aR)-3-(4-Methoxyphenyl)octahydronaphthalen-1(2H)-one
Identifier 35
TLC Rf (EtOAc/hexanes = 1:10) 0.45
¹H NMR (700 MHz, CDCl₃) δ 7.15 – 7.12 (m, 2H), 6.88 – 6.85 (m, 2H), 3.79 (s, 3H), 2.97 (tt, J = 12.8, 3.9 Hz, 1H), 2.58 – 2.45 (m, 2H), 2.05 – 2.00 (m, 1H), 1.96 (dqd, J = 13.3, 4.2, 3.4, 1.9 Hz, 2H), 1.87 – 1.80 (m, 2H), 1.73 (dtd, J = 6.1, 3.0, 1.4 Hz, 1H), 1.67 (dt, J = 13.1, 12.0 Hz, 1H), 1.54 – 1.46 (m, 1H), 1.27 – 1.21 (m, 4H)
¹³C NMR (176 MHz, CDCl₃) δ 211.86, 158.39, 127.54, 55.43, 49.45, 43.76, 43.74, 41.30, 34.41, 25.92, 25.53, 25.21
HRMS Calculated for C₁₇H₂₂NO₂ [M + H]⁺: 259.1698 | Found: 259.1702
Optical rotation [α]ᴅ²⁵ = 31.143 (c = 0.7, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S103–S104
(3R,4aS,8aR)-3-(3,4,5-Trimethoxyphenyl)octahydronaphthalen-1(2H)-one
Identifier 36
TLC Rf (EtOAc/hexanes = 1:4) 0.30
¹H NMR (400 MHz, CDCl₃) δ 6.28 (s, 2H), 3.72 (s, 6H), 3.69 (s, 3H), 2.81 (tt, J = 12.6, 3.9 Hz, 1H), 2.49 – 2.32 (m, 2H), 1.96 – 1.79 (m, 3H), 1.74 – 1.67 (m, 2H), 1.63 – 1.49 (m, 2H), 1.47 – 1.31 (m, 2H), 1.15 – 1.11 (m, 6H)
¹³C NMR (151 MHz, CDCl₃) δ 211.58, 153.45, 140.31, 103.54, 61.00, 56.26, 54.57, 49.45, 44.86, 43.72, 40.91, 34.41, 29.84, 25.91, 25.51, 25.19
HRMS Calculated for C₁₉H₂₆O₄ [M + H]⁺: 319.1909 | Found: 319.1909
Optical rotation [α]ᴅ²⁵ = 17.250 (c = 0.4, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S105–S106
(3S,4aS,8aR)-3-(4-Aminophenyl)octahydronaphthalen-1(2H)-one
Identifier 41
TLC Rf (Et₂O/hexanes = 1:1) 0.45
¹H NMR (400 MHz, CDCl₃) δ 7.00 – 6.94 (m, 2H), 6.68 – 6.64 (m, 2H), 3.51 (t, J = 3.9 Hz, 1H), 2.80 – 2.63 (m, 2H), 2.07 – 1.87 (m, 3H), 1.77 (t, J = 4.4 Hz, 1H), 1.67 – 1.56 (m, 2H), 1.42 – 1.28 (m, 0H), 1.23 – 1.04 (m, 3H)
¹³C NMR (151 MHz, CDCl₃) δ 213.42, 144.41, 135.03, 128.46, 127.59, 127.45, 115.49, 115.27, 55.19, 44.99, 40.19, 39.62, 37.68, 34.27, 29.86, 25.70, 25.65, 25.11
HRMS Calculated for C₁₆H₂₁NO [M + H]⁺: 244.1701 | Found: 214.1703
Optical rotation [α]ᴅ²⁵ = 58.333 (c = 0.3, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S107–S108
(3S,4aS,8aR)-3-(3-Hydroxyphenyl)octahydronaphthalen-1(2H)-one
Identifier 42
TLC Rf (Et₂O/hexanes = 1:2) 0.50
¹H NMR (600 MHz, CDCl₃) δ 7.16 (t, J = 7.9 Hz, 1H), 6.74 (d, J = 7.7 Hz, 1H), 6.69 (d, J = 10.8 Hz, 2H), 5.41 (s, 1H), 3.56 (q, J = 4.1, 3.2 Hz, 1H), 2.84 – 2.69 (m, 2H), 2.07 – 1.89 (m, 4H), 1.83 – 1.59 (m, 4H), 1.38 (qd, J = 11.1, 5.3 Hz, 1H), 1.23 – 1.07 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 213.80, 155.85, 146.74, 129.80, 120.04, 114.59, 113.19, 55.25, 44.67, 40.25, 39.91, 37.88, 34.22, 25.62, 25.58, 25.03
HRMS Calculated for C₁₆H₂₀O₂ [M + H]⁺: 245.1542 | Found: 215.1543
Optical rotation [α]ᴅ²⁵ = 47.833 (c = 0.6, CHCl₃)
NMR spectra Image data were not transcribed
SI, pp. S109–S111
cis-42 and epi-42
Sample composition 1:1 mixture
TLC Rf (Et₂O/hexanes = 1:2) 0.45
¹H NMR (600 MHz, CDCl₃) δ 7.21 – 7.16 (m, 1H), 6.79 (dq, J = 7.6, 1.4 Hz, 1H), 6.72 – 6.68 (m, 2H), 4.95 (d, J = 4.7 Hz, 1H), 3.19 (tt, J = 12.7, 4.0 Hz, 1H, cis-42), 2.97 (tt, J = 12.7, 3.9 Hz, 1H, epi-42), 2.65 (d, J = 5.9 Hz, 1H), 2.63 – 2.40 (m, 2H), 2.34 – 2.22 (m, 1H), 2.12 – 1.89 (m, 3H), 1.87 – 1.78 (m, 1H), 1.78 (s, 0H), 1.56 – 1.43 (m, 2H), 1.36 – 1.15 (m, 2H)
¹³C NMR (151 MHz, CDCl₃) δ 212.13, 212.00, 155.97, 155.95, 146.58, 146.44, 130.01, 129.98, 119.23, 119.06, 113.79, 113.69, 113.65, 54.59, 49.22, 49.02, 48.93, 44.38, 43.74, 40.88, 40.01, 39.08, 34.39, 29.36, 26.36, 25.89, 25.50, 25.21, 25.18, 22.18
HRMS Calculated for C₁₆H₂₀O₂ [M + H]⁺: 245.1542 | Found: 215.1543
Optical rotation [α]ᴅ²⁵ = 24.667 (c = 0.3, CHCl₃)
Single-crystal X-ray diffraction, crystal data CCDC 2551479; identification code: Shenvi418; empirical formula: C₁₆H₂₀O₂; formula weight: 244.32; T = 100.00 K; λ = 0.71073 Å; monoclinic; space group P 1 21 1; a = 5.4607(6) Å, α = 90°; b = 31.648(3) Å, β = 90.111(3)°; c = 14.9734(15) Å, γ = 90°; V = 2587.7(5) ų; Z = 8; calculated density = 1.254 Mg/m³; absorption coefficient = 0.081 mm⁻¹; F(000) = 1056
Single-crystal X-ray diffraction, data collection and refinement Crystal size: 0.2 × 0.04 × 0.03 mm³; θ = 1.287–25.381°; index ranges: −6 ≤ h ≤ 6, −38 ≤ k ≤ 38, −18 ≤ l ≤ 18; reflections collected: 56077; independent reflections: 9491 [R(int) = 0.0779]; completeness to θ = 25.242°: 100.0 %; semi-empirical absorption correction from equivalents; maximum and minimum transmission: 0.7453 and 0.5963; full-matrix least-squares on F²; data/restraints/parameters: 9491/1/655; goodness-of-fit on F²: 1.051; final R indices [I > 2sigma(I)]: R1 = 0.0550, wR2 = 0.1381; R indices (all data): R1 = 0.0707, wR2 = 0.1479; absolute structure parameter: 0.3(6); extinction coefficient: 0.0094(18); largest difference peak and hole: 0.289 and −0.235 e Å⁻³
Single-crystal X-ray diffraction, structural result Four molecules in the asymmetric unit; two isomers, RSR and SSS, are present
Single-crystal X-ray diffraction, crystal size (narrative) 0.200 × 0.040 × 0.30 mm³
Single-crystal X-ray diffraction, R(int) (narrative) 0.779
Single-crystal X-ray diffraction, refinement qualifier Minor non-merohedral twin component observed but not accounted for; pseudo-merohedral twinning detected during refinement with matrix −1 0 0 / 0 −1 0 / 0 0 1
Single-crystal X-ray diffraction molecular-structure images Image data were not transcribed
NMR spectra Image data were not transcribed
SI, pp. S112–S113, S178–S179
epi-43, 43 and cis-43
¹H NMR sample composition 0.2:1:0.6 mixture; CH signals at 2.95, 3.18 and 3.55 ppm
TLC Rf (Et₂O/hexanes = 1:2) 0.40
¹H NMR (400 MHz, CDCl₃) δ 7.11 – 7.00 (m, 2H), 6.83 – 6.72 (m, 2H), 5.40 (s, 1H), 5.09 (s, 0H), 3.55 (dq, J = 7.0, 3.3 Hz, 1H), 3.18 (tt, J = 12.6, 4.0 Hz, 0H), 2.95 (tt, J = 12.6, 4.1 Hz, 0H), 2.83 – 2.69 (m, 1H), 2.64 (s, 0H), 2.60 – 2.51 (m, 0H), 2.51 – 2.38 (m, 0H), 2.25 (d, J = 15.6 Hz, 1H), 2.14 – 1.86 (m, 3H), 1.84 – 1.71 (m, 1H), 1.65 – 1.57 (m, 1H), 1.55 – 1.44 (m, 1H), 1.41 – 1.07 (m, 4H)
¹H NMR spectrum Image data were not transcribed
SI, pp. S114–S115
(3R,4aS,8aR)-3-(Cyclohex-1-en-1-yl)octahydronaphthalen-1(2H)-one
Identifier 37
TLC Rf (EtOAc/hexanes = 1:10) 0.65
¹H NMR (600 MHz, CDCl₃) δ 5.43 (d, J = 4.2 Hz, 1H), 2.39 – 2.25 (m, 3H), 1.99 (dt, J = 6.2, 3.2 Hz, 2H), 1.94 – 1.89 (m, 4H), 1.82 – 1.76 (m, 3H), 1.73 – 1.69 (m, 1H), 1.62 (p, J = 6.2 Hz, 2H), 1.54 (d, J = 6.2 Hz, 2H), 1.48 – 1.29 (m, 2H), 1.19 (h, J = 15.6, 15.0 Hz, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 212.94, 139.94, 120.67, 54.63, 46.85, 46.09, 43.64, 38.57, 34.50, 26.41, 25.95, 25.54, 25.30, 25.21, 23.10, 22.72
HRMS Calculated for C₁₆H₂₄O [M + H]⁺: 233.1905 | Found: 233.1913
Optical rotation [α]ᴅ²⁵ = 11.333 (c = 0.3, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S116–S117
(3R,4aS,8aR)-3-((E)-Prop-1-en-1-yl)octahydronaphthalen-1(2H)-one
Identifier 38
TLC Rf (EtOAc/hexanes = 1:4) 0.66
¹H NMR (600 MHz, CDCl₃) δ 5.50 – 5.28 (m, 2H), 2.45 – 2.33 (m, 2H), 2.16 (td, J = 13.1, 1.3 Hz, 1H), 1.94 – 1.86 (m, 2H), 1.79 (dq, J = 13.1, 2.9 Hz, 3H), 1.70 (ddd, J = 9.0, 4.5, 2.1 Hz, 1H), 1.65 (dd, J = 6.2, 1.4 Hz, 3H), 1.42 – 1.12 (m, 6H)
¹³C NMR (151 MHz, CDCl₃) δ 212.22, 134.69, 124.00, 54.46, 47.98, 43.38, 41.70, 40.01, 34.44, 25.91, 25.53, 25.16, 18.01
HRMS Calculated for C₁₃H₂₀O [M + H]⁺: 193.1592 | Found: 193.1593
Optical rotation [α]ᴅ²⁵ = 21.400 (c = 0.4, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S118–S119
epi-38
TLC Rf (EtOAc/hexanes = 1:4) 0.6
¹H NMR (600 MHz, CDCl₃) δ 5.49 – 5.31 (m, 2H), 2.94 – 2.80 (m, 1H), 2.54 (ddd, J = 13.7, 6.3, 1.2 Hz, 1H), 2.41 (dt, J = 13.7, 2.1 Hz, 1H), 1.90 (tt, J = 11.7, 2.0 Hz, 2H), 1.79 (dq, J = 9.6, 2.4 Hz, 1H), 1.75 – 1.66 (m, 3H), 1.64 (dt, J = 6.0, 1.2 Hz, 3H), 1.61 – 1.51 (m, 2H), 1.27 – 1.09 (m, 4H)
¹³C NMR (151 MHz, CDCl₃) δ 212.45, 133.45, 125.88, 55.33, 45.70, 39.41, 38.53, 38.41, 34.43, 25.88, 25.62, 25.02, 18.22
HRMS Calculated for C₁₃H₂₀O [M + H]⁺: 193.1592 | Found: 193.1599
Optical rotation [α]ᴅ²⁵ = −6.4 (c = 0.11, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S120–S121
(3S,5R)-3-(Furan-3-yl)-5-methylcyclohexan-1-one
Identifier 47
TLC Rf (Et₂O/pentane = 1:4) 0.45
Sample composition Containing 7 % of undesired epi-47
¹H NMR (600 MHz, CDCl₃) δ 7.37 (t, J = 1.7 Hz, 1H), 7.24 (dt, J = 1.7, 0.9 Hz, 1H), 6.31 (dd, J = 1.9, 0.9 Hz, 1H), 2.94 – 2.86 (m, 1H), 2.59 (ddt, J = 13.8, 4.2, 2.1 Hz, 1H), 2.42 (ddt, J = 13.6, 4.1, 2.1 Hz, 1H), 2.30 (td, J = 14.0, 1.1 Hz, 1H), 2.11 (dtt, J = 13.3, 3.6, 2.0 Hz, 1H), 2.04 (td, J = 13.3, 1.1 Hz, 1H), 2.00 – 1.91 (m, 1H), 1.47 – 1.38 (m, 1H), 1.08 (d, J = 6.4 Hz, 3H)
¹³C NMR (151 MHz, CDCl₃) δ 210.49, 143.32, 137.85, 128.80, 109.21, 49.58, 47.73, 41.02, 34.57, 33.18, 22.46
HRMS Calculated for C₁₁H₁₄O₂ [M + H]⁺: 179.1072 | Found: 179.1071
Optical rotation [α]ᴅ²⁵ = 7.093 (c = 0.86, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S123–S124
(3R,5S)-3-(Furan-3-yl)-5-phenylcyclohexan-1-one
Identifier 48
TLC Rf (EtOAc/hexanes = 1:4) 0.7
¹H NMR (600 MHz, CDCl₃) δ 7.39 (d, J = 1.9 Hz, 1H), 7.35 (t, J = 7.7 Hz, 2H), 7.28 – 7.24 (m, 6H), 6.33 (d, J = 1.9 Hz, 1H), 3.14 – 3.02 (m, 2H), 2.72 (ddt, J = 13.9, 4.2, 2.1 Hz, 1H), 2.65 (ddt, J = 13.9, 4.3, 2.1 Hz, 1H), 2.58 (t, J = 13.6 Hz, 1H), 2.47 (t, J = 13.6 Hz, 1H), 2.34 (dt, J = 13.0, 2.6 Hz, 1H), 1.95 (q, J = 12.6 Hz, 1H)
¹³C NMR (151 MHz, CDCl₃) δ 209.64, 143.89, 143.46, 137.97, 128.96, 128.50, 127.09, 126.70, 109.20, 48.63, 47.84, 43.70, 40.23, 34.78, 29.85
HRMS Calculated for C₁₆H₁₆O₂ [M + H]⁺: 241.1229 | Found: 241.1227
Optical rotation [α]ᴅ²⁵ = 11.250 (c = 0.16, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S125–S126
(3R,5S)-3-(Furan-3-yl)-5-isopropylcyclohexan-1-one
Identifier 49
Sample composition Contains 5 % of epi-49
TLC Rf (EtOAc/hexanes = 1:15) 0.3
¹H NMR (600 MHz, CDCl₃) δ 7.38 (t, J = 1.7 Hz, 1H), 7.25 (dt, J = 1.7, 0.9 Hz, 1H), 6.32 (dd, J = 1.9, 0.9 Hz, 1H), 2.87 (tt, J = 12.3, 3.6 Hz, 1H), 2.60 (ddt, J = 13.9, 4.1, 2.1 Hz, 1H), 2.43 (ddt, J = 13.7, 4.1, 2.2 Hz, 1H), 2.33 (td, J = 13.6, 1.1 Hz, 1H), 2.16 – 2.06 (m, 2H), 1.74 – 1.59 (m, 2H), 1.51 – 1.41 (m, 1H), 0.93 (dd, J = 6.8, 4.6 Hz, 6H)
¹³C NMR (600 MHz, CDCl₃) δ 7.38 (t, J = 1.7 Hz, 1H), 7.25 (dt, J = 1.7, 0.9 Hz, 1H), 6.32 (dd, J = 1.9, 0.9 Hz, 1H), 2.87 (tt, J = 12.3, 3.6 Hz, 1H), 2.60 (ddt, J = 13.9, 4.1, 2.1 Hz, 1H), 2.43 (ddt, J = 13.7, 4.1, 2.2 Hz, 1H), 2.33 (td, J = 13.6, 1.1 Hz, 1H), 2.16 – 2.06 (m, 2H), 1.74 – 1.59 (m, 2H), 1.51 – 1.41 (m, 1H), 0.93 (dd, J = 6.8, 4.6 Hz, 6H)
HRMS Calculated for C₁₃H₁₈O₂ [M + H]⁺: 207.1385 | Found: 207.1382
Optical rotation [α]ᴅ²⁵ = −4.000 (c = 0.25, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S127–S128
epi-49
TLC Rf (EtOAc/hexanes = 1:15) 0.3
¹H NMR (600 MHz, CDCl₃) δ 7.36 (t, J = 1.7 Hz, 1H), 7.19 (q, J = 1.3 Hz, 1H), 6.26 – 6.23 (m, 1H), 3.37 (q, J = 5.2 Hz, 1H), 2.65 – 2.55 (m, 2H), 2.37 (ddd, J = 14.1, 4.1, 2.0 Hz, 1H), 2.16 (dd, J = 14.0, 11.1 Hz, 1H), 1.99 (dddt, J = 13.6, 5.1, 3.3, 1.5 Hz, 1H), 1.85 (ddd, J = 13.8, 10.4, 4.2 Hz, 1H), 1.64 (tdt, J = 10.7, 7.5, 3.9 Hz, 1H), 1.57 – 1.48 (m, J = 6.7 Hz, 1H), 0.88 (dd, J = 6.7, 2.9 Hz, 6H)
¹³C NMR (151 MHz, CDCl₃) δ 211.88, 143.37, 139.44, 127.88, 109.60, 45.77, 45.14, 40.01, 33.83, 31.93, 31.70, 19.82, 19.68
HRMS Calculated for C₁₃H₁₈O₂ [M + H]⁺: 207.1385 | Found: 207.1387
Optical rotation [α]ᴅ²⁵ = 28.400 (c = 0.25, CHCl₃)
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S129–S130
(R)-3-(Furan-3-yl)cyclohexan-1-one
Identifier 51
TLC Rf (Et₂O/pentane = 1:1) 0.7
Chiral SFC 98 % ee; 92 % ee when the reaction was performed on a larger scale
¹H NMR (600 MHz, CDCl₃) δ 7.37 (d, J = 1.7 Hz, 1H), 7.23 (s, 1H), 6.30 (d, J = 1.8 Hz, 1H), 3.00 (tt, J = 10.6, 4.0 Hz, 1H), 2.63 (ddt, J = 14.1, 4.1, 1.8 Hz, 1H), 2.48 – 2.27 (m, 3H), 2.18 – 2.01 (m, 2H), 1.82 – 1.69 (m, 2H)
¹³C NMR (151 MHz, CDCl₃) δ 210.79, 143.30, 138.24, 128.60, 109.30, 48.01, 41.36, 35.38, 31.87, 24.91
Optical rotation [α]ᴅ²⁵ = −12.750 (c = 0.4, CHCl₃)
¹H and ¹³C NMR spectra; chiral SFC report Image data were not transcribed
SI, pp. S131–S133
epi-51
Chiral SFC 98 % ee
Optical rotation [α]ᴅ²⁵ = 13.000 (c = 0.4, CHCl₃)
Chiral SFC report Image data were not transcribed
SI, pp. S131, S134
(R)-3-Phenylcyclohexan-1-one
Identifier 52
TLC Rf (Et₂O/pentane = 1:10) 0.5
Chiral SFC 99 % ee
¹H NMR (400 MHz, CDCl₃) δ 7.37 – 7.30 (m, 2H), 7.26 – 7.19 (m, 3H), 3.01 (tt, J = 11.7, 4.0 Hz, 1H), 2.60 (ddd, J = 12.1, 4.6, 2.4 Hz, 1H), 2.58 – 2.52 (m, 1H), 2.51 – 2.32 (m, 2H), 2.21 – 2.04 (m, 2H), 1.92 – 1.71 (m, 2H)
Optical rotation [α]ᴅ²⁵ = 20.000 (c = 0.5, CHCl₃)
Chiral SFC report Image data were not transcribed
SI, pp. S135–S136
epi-52
Chiral SFC 99 % ee
Optical rotation [α]ᴅ²⁵ = −20.222 (c = 0.5, CHCl₃)
Chiral SFC report Image data were not transcribed
SI, pp. S135, S137
2-(4-Chlorobut-1-yn-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
Identifier S8
Sample composition Containing trace amounts of pinacol
Boiling point 120–130 °C at 5 mmHg
¹H NMR (600 MHz, CDCl₃) δ 3.55 (t, J = 7.4 Hz, 2H), 2.68 (t, J = 7.4 Hz, 2H), 1.22 (s, 12H)
¹³C NMR (151 MHz, CDCl₃) δ 99.69, 84.33, 83.10, 83.04, 41.27, 24.67
GC-MS Calculated for C₁₀H₁₆BClO₂ [M]⁺: 214.1 | Found: 214.1
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S138–S139
2-((Z)-4-Chlorobut-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
Identifier S9
Sample and analytical aliquot S9 was obtained as a 10:1 dr clear viscous oil with a small amount (<5 %) of cyclohexyl-derived impurity; at 4.00 g scale, an inseparable 10:1 Z:E mixture was obtained; FC chromatography was performed to get a clean aliquot for analytical data
Boiling point 130 °C at 10 mmHg
TLC Rf (Et₂O/pentane = 1:10) 0.47
¹H NMR (600 MHz, CDCl₃) δ 6.45 (dt, J = 13.8, 7.1 Hz, 1H), 5.52 (dt, J = 13.5, 1.4 Hz, 1H), 3.57 (t, J = 6.8 Hz, 2H), 2.87 (qd, J = 6.9, 1.3 Hz, 2H), 1.27 (s, 11H)
¹³C NMR (151 MHz, CDCl₃) δ 149.45, 121.16, 83.11, 44.39, 34.97, 24.84
HRMS Calculated for C₁₀H₁₆BClO₂ [M + H]⁺: 216.1203 | Found: 216.1207
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S140–S141
((Z)-4-Chlorobut-1-en-1-yl)boronic acid
Identifier 50
¹H NMR (600 MHz, DMSO) δ 6.14 (dt, J = 14.0, 7.1 Hz, 1H), 5.40 (dt, J = 13.6, 1.4 Hz, 1H), 3.59 (t, J = 6.8 Hz, 2H), 2.72 (qd, J = 6.9, 1.4 Hz, 2H)
¹³C NMR (151 MHz, DMSO) δ 145.17, 45.32, 34.78
HRMS Calculated for C₁₂H₁₈B₃Cl₃O₃ [M + H of boroxine]⁺: 368.0607 | Found: 368.0607
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S142–S143
(R,Z)-3-(4-Chlorobut-1-en-1-yl)cyclohexan-1-one
Identifier 53
TLC Rf (Et₂O/pentane = 1:2) 0.6
Chiral SFC 94 % ee
¹H NMR (600 MHz, CDCl₃) δ 5.50 – 5.26 (m, 2H), 3.51 (td, J = 6.8, 4.0 Hz, 2H), 2.82 – 2.72 (m, 1H), 2.51 (qd, J = 6.8, 1.2 Hz, 2H), 2.37 (dddt, J = 18.2, 15.9, 4.2, 1.9 Hz, 2H), 2.28 (dddd, J = 14.0, 12.6, 6.2, 1.3 Hz, 1H), 2.15 (ddd, J = 14.0, 11.8, 1.2 Hz, 1H), 2.08 (dddd, J = 10.0, 7.6, 5.0, 3.1 Hz, 1H), 1.83 (dtt, J = 11.5, 3.8, 1.9 Hz, 1H), 1.78 – 1.67 (m, 1H), 1.51 (dddd, J = 13.5, 12.1, 10.9, 3.6 Hz, 1H)
¹³C NMR (151 MHz, CDCl₃) δ 210.93, 135.76, 125.24, 47.88, 44.15, 41.30, 37.68, 31.73, 30.85, 25.41
HRMS Calculated for C₁₀H₁₅ClO [M + H]⁺: 187.0890 | Found: 187.0890
Optical rotation [α]ᴅ²⁵ = 66.111 (c = 0.9, CHCl₃)
¹H and ¹³C NMR spectra; chiral SFC report Image data were not transcribed
SI, pp. S144–S146
cis-54 and trans-54
Sample composition 1:1 mixture
TLC Rf (Et₂O/pentane = 1:4) 0.8
NMR reporting qualifier Traces of pentane and Et₂O signals were present because the volatile isolated fractions were not fully evaporated
¹H NMR (400 MHz, CDCl₃) δ 5.73 – 5.66 (m, 1H), 5.58 – 5.48 (m, 1H), 2.70 (s, 1H), 2.51 (dt, J = 9.8, 4.8 Hz, 1H), 2.38 (dt, J = 11.7, 4.4 Hz, 2H), 2.34 – 2.20 (m, 1H), 2.20 – 1.98 (m, 3H), 2.05 – 1.62 (m, 3H), 1.58 – 1.39 (m, 1H), 1.35 – 1.18 (m, 1H)
¹³C NMR (151 MHz, CDCl₃) δ 213.36, 212.29, 130.57, 129.80, 128.45, 127.43, 52.22, 48.09, 43.15, 41.60, 40.68, 37.32, 32.09, 30.94, 29.71, 29.61, 26.48, 25.06, 23.36, 23.03, 22.26, 21.02
HRMS Calculated for C₁₀H₁₄O [M + H]⁺: 151.1123 | Found: 151.1122
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S147–S148
(R,Z)-3-(Buta-1,3-dien-1-yl)cyclohexan-1-one
Identifier 54-diene
TLC Rf (Et₂O/pentane = 1:4) 0.65
NMR reporting qualifier Traces of pentane and Et₂O signals were present because the volatile isolated fractions were not fully evaporated
¹H NMR (600 MHz, CDCl₃) δ 6.57 (dddd, J = 16.8, 11.2, 10.2, 1.1 Hz, 1H), 6.00 – 5.90 (m, 1H), 5.30 (ddq, J = 10.7, 9.5, 1.1 Hz, 1H), 5.26 – 5.10 (m, 2H), 2.96 (dddd, J = 14.5, 9.6, 7.2, 4.1 Hz, 1H), 2.39 (ddt, J = 14.1, 4.0, 2.0 Hz, 2H), 2.33 – 2.24 (m, 1H), 2.20 – 2.12 (m, 1H), 2.09 (ddq, J = 13.7, 6.0, 3.7 Hz, 1H), 1.87 (dddt, J = 13.2, 5.5, 3.6, 1.8 Hz, 1H), 1.73 (dtdd, J = 13.6, 12.4, 4.6, 3.5 Hz, 1H), 1.54 – 1.46 (m, 1H), 1.25 (dp, J = 3.7, 1.5 Hz, 10H)
¹³C NMR (151 MHz, CDCl₃) δ 207.13, 134.72, 131.77, 129.08, 118.61, 60.55, 47.91, 41.33, 37.94, 36.06, 31.83, 31.74, 31.08, 29.85, 29.48, 25.42, 22.80, 14.27
HRMS Calculated for C₁₀H₁₄O [M + H]⁺: 151.1123 | Found: 151.1125
¹H and ¹³C NMR spectra Image data were not transcribed
SI, pp. S147, S149–S150
4-(Furan-3-yl)chroman-2-one
Identifier 56
TLC Rf (EtOAc/hexanes = 1:2) 0.7
Chiral SFC 93 % ee
¹H NMR (400 MHz, CDCl₃) δ 7.41 (t, J = 1.7 Hz, 1H), 7.33 – 7.27 (m, 1H), 7.23 – 7.02 (m, 4H), 6.27 (dd, J = 1.9, 1.0 Hz, 1H), 4.25 (t, J = 6.2 Hz, 1H), 3.07 – 2.93 (m, 2H)
¹³C NMR (151 MHz, CDCl₃) δ 167.70, 151.55, 144.26, 139.86, 129.04, 127.93, 125.41, 124.83, 117.41, 109.30, 36.25, 32.00
HRMS Calculated for C₁₃H₁₀O₃ [M + H]⁺: 215.0708 | Found: 215.0706
Optical rotation [α]ᴅ²⁵ = −12.400 (c = 0.25, CHCl₃)
¹H and ¹³C NMR spectra; chiral SFC report Image data were not transcribed
SI, pp. S151–S153
4-(Thiophen-3-yl)chroman-2-one
Identifier 57
TLC Rf (EtOAc/hexanes = 1:2) 0.8
Chiral SFC 98 % ee
¹H NMR (400 MHz, CDCl₃) δ 7.37 – 7.26 (m, 2H), 7.16 – 7.06 (m, 3H), 7.01 – 6.91 (m, 2H), 4.44 (t, J = 6.3 Hz, 1H), 3.07 (dd, J = 6.3, 1.1 Hz, 2H)
¹³C NMR (151 MHz, CDCl₃) δ 167.57, 151.41, 140.86, 128.87, 128.05, 127.12, 126.37, 125.70, 124.70, 122.07, 117.27, 36.49, 36.31, 29.71
HRMS Calculated for C₁₃H₁₀O₂S [M + H]⁺: 231.0480 | Found: 231.0488
Optical rotation [α]ᴅ²⁵ = −17.000 (c = 0.2, CHCl₃)
¹H and ¹³C NMR spectra; chiral SFC report Image data were not transcribed
SI, pp. S154–S156
Methyl (1R,3S,4aR,4bS,6R,8aR,10aR)-3-acetoxy-6-(cyclohex-1-en-1-yl)-10a-methyl-4,8-dioxotetradecahydrophenanthrene-1-carboxylate
Identifier 59
¹H NMR (600 MHz, CDCl₃) δ 5.40 (d, J = 4.1 Hz, 1H), 5.17 (dd, J = 12.2, 7.7 Hz, 1H), 3.71 (d, J = 3.4 Hz, 3H), 2.77 (dd, J = 13.2, 4.1 Hz, 1H), 2.40 – 2.24 (m, 4H), 2.18 – 2.13 (m, 3H), 2.12 – 2.06 (m, 1H), 1.99 – 1.83 (m, 6H), 1.79 – 1.66 (m, 2H), 1.54 – 1.41 (m, 4H), 1.29 – 1.23 (m, 1H), 1.11 (q, J = 11.3 Hz, 1H), 0.83 (s, 3H)
¹H NMR spectrum Image data were not transcribed