A Short and Enantioselective Synthesis of Colletodiol

Abstract

A 12-step enantioselective synthesis of colletodiol has been achieved using a cross-coupling metathesis and a Sharpless ­dihydroxylation as the key steps.

cross-metathesis - colletodiol - Sharpless dihydroxyl­ation

References

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<A NAME="RG12305ST-11">11</A>

This compound gives satisfactory spectroscopic and analytical data.

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<A NAME="RG12305ST-13">13</A>

Dihydroxylation of 12 gives a mixture of 13 and 13′ in a 10:1 ratio (Scheme [3] ).

<A NAME="RG12305ST-14">14</A>

Colletodiol(1): mp 163-165 °C; R _f = 0.35 [toluene-dioxane-AcOH, 20:10:1 (v/v/v)]; [α]_D +35.6 (c 0.5, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 6.73 (m, 2 H), 6.13 (d, J = 15.6 Hz, 1 H), 5.73 (d, J = 15.4 Hz, 1 H), 5.31 (m, 1 H), 5.18 (m, 1 H), 4.07 (dd, J = 8.5, 5.5 Hz, 1 H), 3.67 (dd, J = 8.0, 6.0 Hz, 1 H), 2.87 (br s, OH, 1 H), 2.72 (br s, OH, 1 H), 2.52 (m, 1 H), 2.22 (dt, J = 12.4, 11.4 Hz, 1 H), 2.01 (dd, J = 15.0, 3.5 Hz, 1 H), 1.50 (ddd, J = 15.8, 6.0, 2.0 Hz, 1 H), 1.36 (d, J = 6.5 Hz, 3 H), 1.34 (d, J = 6.8 Hz, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 166.6, 165.1, 146.3, 144.1, 125.7, 123.9, 74.0, 71.9, 68.7, 67.9, 41.1, 36.3, 20.4, 18.1. IR: 3600-3100 (br), 2980, 2934, 1748, 1716, 1653, 1444, 1347, 1314, 1261, 1172, 1105, 1034, 985, 916, 859, 824, 791, 742, 706, 631, 600 cm^-1.