过渡金属催化的不对称O-H,S-H插入反应研究进展

The advance in transition metal-catalyzed asymmetric O-H,S-H insertion reactions

过渡金属催化的卡宾X–H(X=C, O, S, B, Si等)插入反应是一种由简单、易得的卡宾前体快速构建C–X键的最有效方法之一,在合成化学和生物医药领域有着广泛的应用.近20年来,利用过渡金属催化, α-重氮酯、重氮酮、重氮磷酸酯、1,2,3-三氮唑以及非重氮型卡宾前体(如烯炔醛等)对水、醇、酚、羧酸等的O–H键和硫醇、苯硫酚等的S–H键的不对称插入反应研究取得了重要进展,可以高效实现C–O、C–S键的构筑,制备各种具有高附加值的手性α-羟基、巯基、烷氧基/芳氧基以及酰氧基取代的羰基化合物.本文归纳了一些典型的过渡金属催化体系,如双铑(Ⅱ)羧酸、铜/唑啉、钯/双氮配体以及铑(Ⅱ)/手性磷酸(CPA)共催化体系等在卡宾不对称O–H和S–H键插入反应中的应用,探讨了这些催化体系的适应性以及在合成中的应用.

Carbene insertion into the X–H(C,O,S,B,Si,etc.)bond is one of the most effective methods for the rapid construction of C–X bonds from simple and readily available precursors,which has been widely used in synthetic chemistry and biomedicines.In the past two decades,significant progress has been made in the asymmetric insertion reactions ofα-diazoester,α-diazketone,α-diazophosphonate,1,2,3-triazoles and non-diazo carbene precursors(e.g.enynal)to O–H bonds of water,alcohols,phenols and carboxylic acids and S–H bonds of thiols and thiolphenols under transition metal catalysis.The C–O and C–S bonds can be constructed efficiently,and various synthetically important chiralα-hydroxyl,α-mercapto,α-alkoxy/aryloxy andα-acyloxy substituted carbonyl compounds with high optical purities can be prepared.This review focuses on the recent impressive progress and advances in the asymmetric carbene O–H and S–H insertion.The applications of some typical transition metal catalytic systems,such as chiral dirhodium(Ⅱ)carboxylate,copper(Ⅱ)/bisazaferrocene,copper(Ⅰ)/chiral bisoxazoline,palladium(Ⅱ)/chiral dipyridine,and rhodium(Ⅱ)/chiral guanidine complexes as well as rhodium(Ⅱ)/chiral phosphoric acid(CPA)co-catalysis systems are summarized.The scope of these catalytic systems and their potential in synthesis are discussed as well.