含硅路易斯酸的发展及其在有机合成中的应用

综述了含硅路易斯酸R₃SiX X＝I, OTf, NTf₂, C(C₆F₅)Tf₂等]和(R₃SiX＋ML_n)的发展、合成以及它们在有机合成中的应用. 它们主要被用来催化Aldol, 烯丙基化, Diels-Alder, Ene和Friedel-Crafts等反应. 催化剂的用量一般为0.5～20 mol%, 并随着催化剂的活性不同, 反应产率从一般到良好不等. 催化剂活性顺序为R₃SiNTf₂＞R₃SiOTf, (R₃SiX＋ML_n)＞R₃SiX. 也对近年出现的手性含硅路易斯酸的发展和应用进行了概述, 当手性双-(多氟甲磺酰)-亚胺基硅烷用于催化环戊二烯和丙烯酸甲酯的Diels-Alder反应时, ee值高达54%.

Development of Silicon-Based Lewis Acids and Their Applications to Organic Synthesis

This paper mainly describes the development, synthesis and applications of silicon-based Lewis acids R₃SiX X＝I, OTf, NTf₂, C(C₆F₅)Tf₂, etc.] and (R₃SiX＋ML_n). They were principally used to catalyze aldol, allylation, Diels-Alder, ene and Friedel-Crafts reactions. SLAs were used in 0.5～20 mol%, and the yields of the catalyzed reactions varied from moderate to excellent with the different reactivity of silicon-based Lewis acids. The order of the reactivities is R₃SiNTf₂＞R₃SiOTf, (R₃SiX＋ML_n)＞R₃SiX. The development and applications of chiral SLAs are also reviewed. When chiral trialkylsilyl bis(perfluoromethanesulfonyl)imides were used as catalysts for Diels-Alder reaction of cyclopentadiene and methyl acrylate, ee value of the reaction was up to 54%.