Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA.
Chemistry. 2012 Dec 14;18(51):16498-509. doi: 10.1002/chem.201202085. Epub 2012 Oct 23.
The development of a general and practical zinc-catalyzed enantioselective alkyne addition methodology is reported. The commercially available ProPhenol ligand (1) has facilitated the addition of a wide range of zinc alkynylides to aryl, aliphatic, and α,β-unsaturated aldehydes in high yield and enantioselectivity. New insights into the mechanism of this reaction have resulted in a significant reduction in reagent stoichiometry, enabling the use of precious alkynes and avoiding the use of excess dimethylzinc. The enantioenriched propargylic alcohols from this reaction serve as versatile synthetic intermediates and have enabled efficient syntheses of several complex natural products.
本文报道了一种通用且实用的锌催化对映选择性炔加成方法的发展。商业可得的 ProPhenol 配体（1）促进了锌炔基试剂与芳基、脂肪族和α,β-不饱和醛的加成反应，具有高产率和对映选择性。对该反应机理的新见解导致试剂化学计量显著减少，从而能够使用昂贵的炔烃并避免使用过量的二甲基锌。该反应得到的手性炔丙醇是多功能的合成中间体，并实现了几种复杂天然产物的高效合成。
