| Abstract
| - By the catalysis of AK or porcine pancreas lipases,3-iodo-2-phenyl-1,2-propanediol, 1-(hydroxymethyl)-1-phenyloxirane, 2-(iodomethyl)-4-phenyl-3-butyne-1,2-diol,2-(iodomethyl)-4-(trimethylsilyl)-3-butyne-1,2-diol, and5,5-dimethyl-2-(iodomethyl)-3-hexyne-1,2-diol were resolved in veryhighenantioselectivities (E ≥ 153). The obtainedenantiomerically pure or optically enriched compounds,containing an iodo atom, an oxirane moiety, or an alkynyl group, areversatile building blocks forthe synthesis of chiral azido diols, sulfanyl diols, cyano diols, theside chain of a vitamin D3metabolite, the ω-chain of a prostaglandin analog, and an aggregationpheromone (1S,5R)-(−)-frontalin. Models based on the consideration of the importance ofsize, distance, and electron effectare proposed to interpret the observed stereospecificity in theenzymatic reactions. Thus, the lipase-catalyzed reactions of 1,1-disubstituted 1,2-diols occurred efficientlyat the primary hydroxyl groupswhile the enantioselectivity was controlled by the tertiary carbinylcenters.
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