A Direct Entry to Carbasugars: Asymmetric Synthesis of 1-epi-(+)-MK7607

Abstract

A short and flexible synthesis of 5a-carbasugars is presented. The combination of a proline-catalyzed aldol reaction and a ring-closing metathesis affords 1-epi-(+)-MK7607 in seven steps with an overall yield of 23%.

carbasugars - organocatalysis - asymmetric synthesis - aldol reaction - ring-closing metathesis

References and Notes

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<A NAME="RG29006ST-19">19</A>

Analytical Data of 3.
R _f = 0.15 (EtOAc-MeOH = 6:1); [α]_D ²² 232.7 (c 1.25, H₂O). ¹H NMR (300 MHz, D₂O): δ = 3.49 (dd, J = 10.9, 4.2 Hz, 1 H), 3.59 (dd, J = 10.9, 7.4 Hz, 1 H), 4.03 (m, 1 H), 4.09 (m, 2 H, CH₂OH), 4.16 (d, J = 4.2 Hz, 1 H), 5.66 (m, 1 H, C=CH) ppm. ¹³C NMR (75 MHz, D₂O): δ = 61.8 (CH₂OH), 66.5, 70.7, 71.7, 72.3 (CHOH), 126.9 (C=CH), 137.5 (C=CH). MS (EI, 70 eV): m/z (%) = 140 (7), 122 (10), 116 (47), 111 (28), 99 (17), 98 (100), 97 (21), 83 (11), 81 (13), 71 (11), 72 (14), 69 (27), 55 (15). HRMS: m/z calcd for C₇H₁₂O₅ - 2H₂O [M⁺ - 2H₂O]: 140.04734; found: 140.04735.