Compound characterization data — Curran et al., 2026

Millie C. Curran, James M. Jeffries, Bartosz Kowalski, Natasha E. Hatton, Gavin H. Thomas, Martin A. Fascione. “Expediting chemoenzymatic access to bacterial ‘sialic acid-like’ sugars via mapping of wild type sialic acid aldolase enzyme substrate tolerance and promiscuity.” ChemRxiv (2026). https://doi.org/10.26434/chemrxiv.15007810/v1

Benzyl-α-L-fucopyranoside
Identifier	SI-2
¹H NMR (400 MHz, methanol-d₄)	δ 7.31 (d, J = 6.9 Hz, 31H, ArH), 4.85 (d, J = 2.7 Hz, 1H, H1), 4.67 (d, J = 11.9 Hz, 1H, CHaHbPh), 4.54 (d, J = 12.4 Hz, 1H, CHaHbPh), 3.97 – 3.90 (m, 1H, H5), 3.76 (t, J = 2.5 Hz, 2H, H3), 3.64 (d, J = 2.3 Hz, 1H, H2), 3.60 – 3.54 (m, 1H, H4), 1.17 (d, J = 6.9 Hz, 3H, H6)
¹³C NMR	No carbon NMR as carried on as crude
HRMS (ESI)	calcd for C₁₃H₁₈O₅ [M+Na]⁺ 277.1042, found 277.1046
¹H NMR spectrum	Image data were not transcribed

Benzyl 3,4-O-isopropylidene-α-L-fucopyranoside
Identifier	SI-3
¹H NMR (600 MHz, chloroform-d)	δ 7.29 – 7.15 (m, 5H, Ar-H), 4.86–4.81 (m, 1H, H-1), 4.68 (d, J = 11.8 Hz, 1H, CHaHbPh), 4.47 (d, J = 11.9 Hz, 1H, CHaHbPh), 4.15–4.09 (m, 1H, H-3), 4.06 (td, J = 6.7, 2.3 Hz, 1H, H-5), 3.95 (dd, J = 6.0, 2.4 Hz, 1H, H-4), 3.77 – 3.72 (m, 1H, H-2), 1.41 (s, 3H, Me-ISP), 1.25 (s, 3H, Me-ISP), 1.21 (d, J = 6.9 Hz, 3H, H-6)
¹³C NMR (151 MHz, CDCl₃)	δ 141.01 (C=O), 128.67 (Ar-C), 127.77 (Ar-C), 127.11 (Ar-C), 109.35 (C(CH₃)₂), 97.06 (C1), 76.26 (C3), 75.77 (C4), 69.85 (CH₂Ph), 69.95 (C2), 64.24 (C5), 27.86 (Me-ISP), 26.02 (Me-ISP), 16.36 (C6)
HRMS (ESI)	calcd for C₁₆H₂₂O₅ [M+Na]⁺ 317.1357, found 317.1459
¹H NMR spectrum	Image data were not transcribed

Benzyl 2-O-acetyl-3,4-O-isopropylidene-α-L-fucopyranoside
Identifier	SI-4
¹H NMR (400 MHz, chloroform-d)	δ 7.38 – 7.29 (m, 5H, Ar-H), 4.99 (d, J = 3.6 Hz, 1H, H-1), 4.90 (dd, J = 8.3, 3.6 Hz, 1H, H-2), 4.70 (d, J = 12.4 Hz, 1H, CHaHbPh), 4.52 (d, J = 12.4 Hz, 1H, CHaHbPh), 4.36 (dd, J = 8.2, 5.3 Hz, 1H, H-3), 4.17 (dd, J = 6.7, 2.4 Hz, 1H, H-5), 4.09 (dd, J = 5.3, 2.6 Hz, 1H, H-4), 2.09 (s, 2H, Ac), 1.53 (s, 2H, CH₃-ISP), 1.36 – 1.34 (m, 5H, H6 + CH₃-ISP)
¹³C NMR (101 MHz, chloroform-d)	δ 170.66 (Ac), 137.36 (ArC), 128.51 (ArC), 127.98 (ArC), 127.74 (ArC), 109.43 (C(CH₃)₂), 95.51 (C-1), 76.23 (C-4), 73.47 (C-3), 72.05 (C-2), 69.71 (OCH₂Ph), 63.47 (C-5), 28.13 (CH₃-ISP), 26.50 (CH₃-ISP), 21.09 (Ac), 16.36 (C-6)
HRMS (ESI)	calcd for C₁₈H₂₄O₆ [M+Na]⁺ 359.1464, found 359.1465
¹H and ¹³C NMR spectra	Image data were not transcribed

Benzyl 2-O-acetyl-3,4-di-O-methanesulfonyl-α-L-fucopyranoside
Identifier	SI-5
¹H NMR (400 MHz, chloroform-d)	δ 7.40 – 7.29 (m, 5H, Ar-H), 5.16 – 5.08 (m, 3H, H-1, H-2, H-3), 5.04 – 5.01 (m, 1H, H-4), 4.69 (d, J = 12.2 Hz, 1H, CHaHbPh), 4.56 (d, J = 12.2 Hz, 1H, CHaHbPh), 4.18 – 4.09 (m, 1H, H-5), 3.19 (d, J = 0.7 Hz, 3H, Ms), 3.11 (s, 3H, Ms), 2.08 (s, 3H, Ac), 1.28 (d, J = 6.5 Hz, 2H, H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 169.84 (Ac C=O), 136.77 (ArC), 128.70 (ArC), 128.39 (ArC), 128.16 (ArC), 95.44 (C-1), 80.66 (C-4), 74.46 (C-3), 70.42 (CH₂Ph), 67.81 (C-2), 64.94 (C-5), 39.17 (Ms), 38.73 (Ms), 20.84 (Ac), 16.47 (C-6)
HRMS (ESI)	calcd for C₁₇H₂₄O₁₀S₂ [M+Na]⁺ 475.0703, found 475.0703
¹H and ¹³C NMR spectra	Image data were not transcribed

Benzyl 2-O-acetyl-4-azido-4,6-dideoxy-3-O-mesyl-α-L-glucopyranoside
Identifier	SI-6
¹H NMR (400 MHz, chloroform-d)	δ 7.38 – 7.29 (m, 4H, Ar-H), 5.01 (d, J = 3.4 Hz, H, C-1), 4.98 (d, J = 9.7 Hz, 1H, H-3), 4.89 (dd, J = 10.0, 3.7 Hz, 1H, H-2), 4.69 (d, J = 12.4 Hz, 1H, CHaHbPh), 4.53 (d, J = 12.4 Hz, 1H, CHaHbPh), 3.80 – 3.71 (m, 1H, H-5), 3.23 (t, J = 9.8 Hz, 1H, H-4), 3.11 (s, 3H, Ms), 2.09 (s, 3H, Ac), 1.34 (d, J = 6.2 Hz, 3H, H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 170.20 (Ac), 136.76 (ArC), 128.61 (ArC), 128.25 (ArC), 128.00 (ArC), 95.19 (C-1), 78.49 (C-3), 70.57 (C-2), 70.02 (CH₂Ph), 66.80 (C-4), 66.48 (C-5), 39.09 (Ms), 20.85 (Ac), 18.27 (C-6)
HRMS (ESI)	calcd for C₁₆H₂₁N₃O₇S [M+Na]⁺ 402.0996, found 402.0992
¹H and ¹³C NMR spectra	Image data were not transcribed

Benzyl 2,3-anhydro-4-azido-4,6-dideoxy-α-L-allopyranoside
Identifier	SI-7
¹H NMR (400 MHz, chloroform-d)	δ 7.40 – 7.28 (m, 5H, Ar-H), 5.00 (dd, J = 3.2, 0.6 Hz, 1H, H-1), 4.77 (d, J = 12.3 Hz, 1H, CHaHbPh), 4.64 (d, J = 12.3 Hz, 1H, CHaHbPh), 3.95 (dq, J = 9.6, 6.3 Hz, 1H, H-5), 3.54 (d, J = 1.6 Hz, 1H, H-3), 3.48 (dd, J = 4.1, 3.2 Hz, 1H, H-2), 3.15 (dd, J = 9.6, 1.6 Hz, 1H, H-4), 1.22 (d, J = 6.3 Hz, 3H, H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 137.54 (ArC), 128.62 (ArC), 128.27 (ArC), 128.04 (ArC), 92.18 (C-1), 69.67 (CH₂Ph), 63.34 (C-5), 61.67 (C-4), 53.86 (C-2), 52.44 (C-3), 17.99 (C-6)
HRMS (ESI)	calcd for C₁₃H₁₅N₃O₃ [M+Na]⁺ 284.1008, found 284.1006
¹H and ¹³C NMR spectra	Image data were not transcribed

Benzyl 2,4-diazido-2,4,6-trideoxy-α-L-altropyranoside
Identifier	SI-8
¹H NMR (400 MHz, chloroform-d)	δ 7.42 – 7.31 (m, 5H, Ar-H), 4.88 (d, J = 1.7 Hz, 1H, H-1), 4.77 (d, J = 11.7 Hz, 1H, CHaHbPh), 4.58 (d, J = 11.7 Hz, 1H, CHaHbPh), 4.12 – 4.01 (m, 2H, H-3 and H-5), 3.84 (dd, J = 4.0, 1.9 Hz, 1H, H-2), 3.44 (dd, J = 9.9, 2.3 Hz, 1H, OH), 3.22 (dd, J = 9.8, 3.1 Hz, 1H, H-4), 1.37 (d, J = 6.3 Hz, 3H, H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 128.91 (ArC), 128.70 (ArC), 128.42 (ArC), 97.00 (C-1), 70.43 (CH₂Ph), 69.57 (C-3), 63.22 (C-5), 61.44 (C-4), 60.97 (C-2), 18.29 (C-6)
HRMS (ESI)	calcd for C₁₃H₁₆N₆O₃ [M+Na]⁺ 327.1180, found 327.1176
¹H and ¹³C NMR spectra	Image data were not transcribed

Benzyl 3-O-acetyl-2,4-diazido-2,4,6-trideoxy-α-L-altropyranoside
Identifier	SI-9
¹H NMR (400 MHz, chloroform-d)	δ 7.39 – 7.29 (m, 5H, ArH), 5.07 (ddd, J = 6.0, 3.7, 0.6 Hz, 1H, H-3), 4.81 – 4.75 (m, 2H, CHaHbPh), 4.53 (d, J = 11.9 Hz, 1H, CHaHbPh), 4.20 – 4.09 (m, 1H, H-5), 3.92 (dd, J = 5.9, 3.2 Hz, 1H, H-2), 3.49 (dd, J = 8.1, 3.7 Hz, 1H, H-4), 2.10 (s, 3H, Ac), 1.33 (d, J = 6.5 Hz, 2H, H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 170.27 (Ac C=O), 137.12 (ArC), 128.61 (ArC), 128.11 (ArC), 127.83 (ArC), 97.24 (C-1), 70.09 (CH₂Ph, 70.03 (C-3), 65.51 (C-5), 60.43 (C-4), 59.76 (C-2), 20.85 (Ac), 18.19 (C-6)
HRMS (ESI)	calcd for C₁₅H₁₈N₆O₄ [M+Na]⁺ 369.1280, found 369.1282
¹H and ¹³C NMR spectra	Image data were not transcribed

Benzyl 2,4-diacetamido-2,4,6-trideoxy-α-L-altropyranoside
Identifier	SI-11
¹H NMR (400 MHz, chloroform-d)	δ 7.41 – 7.28 (m, 4H, Ar-H), 6.11 (d, J = 9.0 Hz, 1H, NHAc), 5.96 (dt, J = 9.2, 5.5 Hz, 1H, NHAc), 4.79 (s, 1H, H-1), 4.70 (d, J = 11.6 Hz, 1H, CHaHbPh), 4.54 (d, J = 11.7 Hz, 1H, CHaHbPh), 4.41 (dq, J = 8.8, 1.3 Hz, 1H, H-2), 3.95 (dd, J = 10.8, 8.8 Hz, 1H, H-4), 3.82 (dq, J = 10.3, 6.2 Hz, 1H, H-5), 3.72 (d, J = 1.6 Hz, 2H, H-3), 1.99 (d, J = 1.0 Hz, 6H, 2 x Ac), 1.25 (d, J = 6.2 Hz, 3H, H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 170.12 (C=O), 169.64 (C=O), 136.05 (ArC), 128.85 (ArC), 128.56 (ArC), 128.29 (ArC), 98.36 (C-1), 70.22 (CH₂Ph), 69.24 (C-3), 64.25 (C-5), 50.11 (C-2), 49.87 (C-4), 23.58 (Ac), 23.43 (Ac), 17.96 (C-6)
HRMS (ESI)	calcd for C₁₇H₂₄N₂O₅ [M+Na]⁺ 359.1577, found 359.1577
¹H and ¹³C NMR spectra	Image data were not transcribed

2,4-Di-N-acetamido-2,4,6-trideoxy-L-altropyranose
Identifier	6
¹H NMR (400 MHz)	δ 5.23 (d, J = 2.1 Hz, 1H, H-1), 4.06 (dd, J = 3.6, 1.9 Hz, 1H, H-2), 3.94 – 3.84 (m, 2H, H-3. H-5), 3.78 (dd, J = 10.4, 3.0 Hz, 1H, H-4), 2.05 (s, 3H, NHAc), 1.99 (s, 2H, NHAc), 1.17 (d, J = 6.1 Hz, 3H, H-6)
¹³C NMR (101 MHz, D₂O)	δ 174.87 (C=O), 174.10 (C=O), 90.57 (C-1), 69.41 (C-3), 68.09 (C-5), 53.55 (C-2), 50.72 (C-4), 21.97 (2C, 2 x NHAc), 17.22 (H-6)
HRMS (ESI)	calcd for C₁₀H₁₈N₂O₅ [M+Na]⁺ 269.1109, found 269.1108
¹H and ¹³C NMR spectra	Image data were not transcribed

2,4-Diazido-2,4,6-trideoxy-L-altropyranose
Identifier	8
α¹C₄:β⁴C₁	2:1
TLC (PE:EtOAc, 7:3 v/v)	Rf 0.3
¹H NMR (400 MHz, methanol-d₄)	δ 5.24 (d, J = 1.5 Hz, 1H, α¹C₄ H-1), 4.83 (d, J = 5.4 Hz, 1H, β⁴C₁ H-1), 4.18 (qd, J = 6.9, 5.1 Hz, 1H, β⁴C₁ H-5), 4.08 (dd, J = 3.8, 2.9 Hz, 1H, α¹C₄ H-3), 3.98 (dd, J = 7.8, 3.9 Hz, 1H, β⁴C₁ H-3), 3.96 – 3.90 (m, 1H, α¹C₄ H-5), 3.65 (dd, J = 3.9, 1.6 Hz, 1H, α¹C₄ H-2), 3.55 (dd, J = 7.8, 5.5 Hz, 1H, β⁴C₁ H-2), 3.50 (dd, J = 5.2, 3.6 Hz, 1H, β⁴C₁ H-4), 3.03 (dd, J = 9.9, 2.9 Hz, 1H, α¹C₄ H-4), 1.30 (d, J = 2.8 Hz, 3H, CH₃), 1.28 (d, J = 2.2 Hz, 3H, CH₃)
¹³C NMR (101 MHz, methanol-d₄)	δ 93.45 (α¹C₄ C-1), 93.39 (β⁴C₁ C-1), 70.40 (α¹C₄ C-3), 70.24 (β⁴C₁ C-3), 69.32 (α¹C₄ C-5), 68.84 (β⁴C₁ C-5), 65.87 (β⁴C₁ C-2), 65.70 (α¹C₄ C-2), 65.12 (β⁴C₁ C-4), 62.78 (α¹C₄ C-4), 19.00 (C-6), 17.55 (C-6)
¹H and ¹³C NMR spectra	Image data were not transcribed

α-p-Methoxy phenyl-2,3,4-tri-O-acetyl-D-fucopyranoside
Identifier	SI-13
¹H NMR (400 MHz, chloroform-d)	δ 6.98 (d, J = 9.1 Hz, 2H, Ar-H), 6.83 (d, J = 9.1 Hz, 2H, Ar-H), 6.77 (d, J = 1.9 Hz, 2H, Ar-H), 5.62 (dd, J = 1447.0, 3.7 Hz, 1H, H-1), 5.57 (dd, J = 10.9, 3.4 Hz, 1H, H-3), 5.36 (dd, J = 3.5, 1.3 Hz, 1H, H-4), 5.25 (dd, J = 10.9, 3.7 Hz, 1H, H-2), 4.31 (qd, J = 6.5, 1.4 Hz, 1H, H-5), 3.77 (s, 3H, OPMP-OMe), 2.19 (s, 3H, OAc), 2.07 (s, 3H, OAc), 2.02 (s, 3H, OAc), 1.13 (d, J = 6.5 Hz, 3H, H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 170.80 (C=O), 170.68 (C=O), 170.34 (C=O), 155.33 (ArC), 150.77 (ArC), 117.90 (ArC), 114.82 (ArC), 95.79 (C1), 71.19 (C4), 68.14 (C2), 68.09 (C3), 65.35 (C5), 55.81 (OMe), 20.95 (Ac-CH₃), 20.89 (Ac-CH₃), 20.81 (Ac-CH₃), 16.02 (C6)
HRMS (ESI)	calcd for C₁₀H₁₈N₂O₅ [M+Na]⁺ 419.1317, found 419.1313
¹H and ¹³C NMR spectra	Image data were not transcribed

β-p-Methoxy phenyl-2,3,4-tri-O-acetyl-D-fucopyranoside
Identifier	SI-13
¹H NMR (400 MHz, chloroform-d)	δ 6.95 (d, J = 9.1 Hz, 2H, ArH), 6.81 (d, J = 9.1 Hz, 2H, ArH), 5.43 (dd, J = 10.5, 8.0 Hz, 1H, H-2), 5.35 – 5.27 (m, 2H, H-4), 5.08 (dd, J = 10.5, 3.4 Hz, 1H, H-3), 4.91 (dd, J = 8.0, 0.0 Hz, 1H, H-1), 3.91 (qd, J = 6.4, 1.1 Hz, 1H, H-5), 3.77 (d, J = 0.8 Hz, 3H, PMP-OMe), 2.20 (s, 3H, Ac), 2.07 (s, 3H, Ac), 2.01 (s, 3H, Ac), 1.27 (d, J = 6.4 Hz, 3H, H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 170.86 (C=O), 170.39 (C=O), 169.66 C=O), 155.71 (ArC), 151.40 (ArC), 118.65 (ArC), 114.67 (ArC), 100.88 (C1), 71.41 (C3), 70.22 (C4), 69.57 (C5), 69.01 (C2), 55.78 (OMe), 20.95 (Ac-CH₃), 20.86 (Ac-CH₃), 20.79 (Ac-CH₃), 16.30 (C6)
HRMS (ESI)	calcd for C₁₀H₁₈N₂O₅ [M+Na]⁺ 419.1317, found 419.1313
¹H and ¹³C NMR spectra	Image data were not transcribed

p-Methoxyphenyl-3-O-benzoyl-D-fucopyranoside
Identifier	SI-14
¹H NMR (400 MHz, chloroform-d)	δ 8.12 (dddd, J = 8.3, 4.7, 1.8, 0.8 Hz, 5H, ArH), 7.63 – 7.56 (m, 2H, ArH), 7.51 – 7.44 (m, 6H, ArH), 7.09 – 7.02 (m, 4H, ArH), 6.89 – 6.81 (m, 4H, ArH), 5.56 – 5.48 (m, 2H, α H-1, H-3), 5.16 (ddt, J = 10.1, 3.2, 0.8 Hz, 1H, β H-3), 4.87 (dt, J = 7.7, 0.8 Hz, 1H, β H-1), 4.33 – 4.25 (m, 2H, α H-2, H-5), 4.22 (ddd, J = 10.1, 7.8, 2.6 Hz, 1H, β H-2), 4.09 (d, J = 16.7 Hz, 2H, α H-4), 4.03 (s, 1H, β H-4), 3.93 – 3.84 (m, 1H, β H-5), 3.80 – 3.76 (m, 6H, both OPMP-OMe), 1.39 (dd, J = 6.5, 0.9 Hz, 3H, β H-6), 1.32 – 1.28 (m, 3H, α H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 133.62 (ArC), 130.05 (ArC), 128.66 (ArC), 118.86 (ArC), 118.11 (ArC), 114.86 (ArC), 114.69 (ArC), 102.80 (β C-1), 98.73 (α C-1), 76.16 (β C-3), 74.49 (α C-3), 70.98 (α C-5), 70.91 (β C-5), 70.24 (β C-4), 69.33 (β C-2), 67.29 (α C-4), 66.86 (α C-2), 55.81 (both OPMP-OMe), 16.40 (α C-6), 16.18 (β C-6)
HRMS (ESI)	calcd for C₂₀H₂₂O₇ [M+Na]⁺ 397.1272, found 397.1258
¹H and ¹³C NMR spectra	Image data were not transcribed

α-p-Methoxyphenyl-2,4-diazido-3-O-benzoyl-6-deoxy-D-mannopyranoside
Identifier	SI-15
¹H NMR (400 MHz, chloroform-d)	δ 8.18 – 8.12 (m, 2H, Bz ArH), 7.67 – 7.61 (m, 1H, Bz ArH), 7.51 (dd, J = 8.3, 7.1 Hz, 2H, Bz ArH), 7.02 (d, J = 9.1 Hz, 2H, PMP ArH), 6.85 (d, J = 9.1 Hz, 1H, PMP ArH), 5.72 (dd, J = 10.0, 3.7 Hz, 1H, H3), 5.40 (d, J = 1.8 Hz, 1H, H-1), 4.38 (dd, J = 3.7, 1.8 Hz, 1H, H-2), 3.88 – 3.80 (m, 1H, H-5), 3.78 (s, 3H, PMP-OMe), 3.76 (t, 1H, H-4), 1.38 (d, J = 6.1 Hz, 3H, H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 133.99 (Bz ArC), 130.19 (Bz ArC), 128.83 (Bz ArC), 117.70 (PMP ArC), 114.87 (PMP ArC), 97.11 (C-1), 72.60 (C-3), 67.94 (C-5), 63.15 (C-4), 61.41 (C-2), 55.80 (PMP-OMe), 18.55 (C-6)
HRMS (ESI)	calcd for C₂₀H₂₀N₆O₆ [M+Na]⁺ 447.1390, found 447.1387
¹H and ¹³C NMR spectra	Image data were not transcribed

β-p-Methoxyphenyl-2,4-diazido-3-O-benzoyl-6-deoxy-D-mannopyranoside
Identifier	SI-15
¹H NMR (400 MHz, chloroform-d)	δ 8.13 (dd, J = 8.4, 1.4 Hz, 2H, Bz ArH), 7.67 – 7.61 (m, 1H, Bz ArH), 7.51 (dd, J = 8.3, 7.2 Hz, 2H, Bz ArH), 6.99 (d, J = 9.1 Hz, 2H, PMP ArH), 6.84 (d, J = 9.1 Hz, 2H, PMP ArH), 5.15 (d, J = 1.2 Hz, 1H, H-1), 5.14 – 5.11 (m, 1H, H-3), 4.47 (td, J = 3.6, 1.3 Hz, 1H, H-2), 3.78 (s, 3H, PMP-OMe), 3.72 (t, J = 10.0 Hz, 1H, H-4), 3.42 (dd, J = 9.7, 6.1 Hz, 1H, H-5), 1.49 (d, J = 6.1 Hz, 3H, H-6)
¹³C NMR (101 MHz, chloroform-d)	δ 134.02 (Bz ArC), 130.13 (Bz ArC), 128.78 (Bz ArC), 118.42 (PMP ArC), 114.68 (PMP ArC), 98.60 (C-1), 73.93 (C-3), 71.55 (C-5), 62.43 (C-4), 61.89 (C-2), 55.72 (PMP-OMe), 18.56 (C-6)
HRMS (ESI)	calcd for C₂₀H₂₀N₆O₆ [M+Na]⁺ 447.1390, found 447.1387
¹H and ¹³C NMR spectra	Image data were not transcribed

2,4-Diazido-2,4,6-trideox-D-mannose
Identifier	7
¹H NMR (400 MHz, D₂O)	δ 5.22 (d, J = 1.8 Hz, 1H, H-1 S1), 4.96 (d, J = 1.4 Hz, 1H, H-1 S2), 4.12 (dd, J = 10.0, 3.8 Hz, 1H, H-3 S1), 4.05 (dd, J = 3.8, 1.3 Hz, 1H, H-2 S2), 4.00 (dd, J = 3.8, 1.7 Hz, 1H, H-2 S1), 3.93 (d, J = 3.7 Hz, 1H, H-3 S2), 3.91 (d, J = 3.7 Hz, 1H, H-5 S2), 3.82 (dq, J = 9.8, 6.2 Hz, 1H, H-5 S1), 3.42 – 3.33 (m, 3H, H-4 S1), 3.28 (t, J = 9.8 Hz, 1H, H-4 S2), 1.39 – 1.29 (m, 11H, H-6 both)
¹³C NMR (101 MHz, D₂O)	δ 92.85 (C1 S2), 92.15 (C1 S1), 71.86 (C5 S2), 71.04 (C3 S2), 69.27 (C3 S1), 65.71 (C2 S2), 65.04 (C4 S1), 64.52 (C4 S2), 64.07 (C2 S1), 17.42 (d, J = 4.5 Hz, C6 both)
HRMS (ESI)	calcd for C₆H₁₀N₆O₃ [M+Na]⁺ 237.0721, found 237.0707
¹H and ¹³C NMR spectra	Image data were not transcribed

6-deoxy-2,4-ManDiNAc
Identifier	5
¹H NMR (400 MHz, D₂O)	δ 5.10 (d, J = 1.6 Hz, 1H, α H-1), 4.95 (d, J = 1.7 Hz, 1H, β H-1), 4.46 (dd, J = 4.4, 1.7 Hz, 1H, β H-2), 4.29 (dd, J = 4.6, 1.6 Hz, 1H, α H-2), 4.05 (dd, J = 10.7, 4.6 Hz, 1H, α H-3), 4.01 – 3.92 (m, 1H, α H-5), 3.82 (dd, J = 10.8, 4.3 Hz, 1H, β H-3), 3.77 (t, J = 10.5 Hz, 1H, α H-4), 3.66 (t, J = 10.4 Hz, 1H, β H-4), 3.49 (dq, J = 10.0, 6.2 Hz, 1H, β H-5), 2.11 (s, 3H, β OAc), 2.06 (s, 3H, α OAc), 2.02 (d, J = 2.6 Hz, 6H, α and β 2 x OAc), 1.21 (d, J = 6.2 Hz, 3H, β H-6), 1.18 (d, J = 6.3 Hz, 3H, α H-6)
¹³C NMR (101 MHz, D₂O)	δ 92.79 (α and β C-1), 71.63 (β C-5), 70.02 (β C-3), 67.04 (α C-5), 66.58 (α C-3), 53.59 (β C-2 and α C-4), 53.22 (α C-4), 52.76 (α C-2), 22.16 (3 x Ac), 21.96 (Ac), 16.85 (2 x C-6)
HRMS (ESI)	calcd for C₁₀H₁₈N₂O₅ [M+Na]⁺ 269.1108, found 269.1108
¹H and ¹³C NMR spectra	Image data were not transcribed

Leg5Ac7Ac
Identifier	1
¹H NMR (500 MHz, D₂O)	δ 4.21 (d, J = 10.4 Hz, 1H, H-6), 3.97 – 3.88 (m, 1H, H-4), 3.84 (d, J = 5.3 Hz, 2H, H-7 + H-8), 3.70 (t, J = 10.1 Hz, 1H, H-5), 2.20 (d, J = 12.8 Hz, 1H, H3 eq.), 1.99 (s, 3H, Ac), 1.98 (s, 3H, Ac), 1.78 (m, 1H, H-3 ax.), 1.14 (d, J = 5.5 Hz, 3H, H-9)
¹³C NMR (151 MHz, D₂O)	δ 175.72 (C=O), 175.12 (C=O), 175.01 (C=O), 70.69 (C-6), 68.86 (C-4), 67.64 (C-8), 54.53 (C-7), 54.04 (C-5), 23.33 (Ac), 22.97 (Ac), 20.40 (C-9), 96.95 (C2, low S/N), 40.55 (C3, low S/N)
¹H and ¹³C NMR spectra	Image data were not transcribed

Crude Pse5Az7Az
Identifier	10
¹H NMR	H-3ax: apparent triplet at 2.01 ppm, ³J coupling constant ~12.5 Hz between H-3ax and H-4 and ²J coupling constant ~12 Hz between H-3ax and H-3eq; H-3eq: double doublet at 1.92 ppm, ³J coupling constant ~5 Hz between H-3eq and H-4 and ²J coupling constant ~12.5 Hz between H-3ax and H-3eq
¹H NMR spectrum	Image data were not transcribed

Aldolase reaction mixtures
¹H NMR time-course spectra and LCMS chromatograms	Image data were not transcribed