Demonstrated herein are two conceptually different approaches for enantioselective activation of S-H and Si-H bonds, by using protein-conjugated iron complexes for catalyzing the reactions of carbenoids with either racemic thiol or non-chiral silane to form enantiomerically enriched products. Catalysts examined were native myoglobin and transferrin and the spontaneously formed conjugates of serum albumins with properly designed iron(III) corroles. Reactions proceed very fast in all cases and lead to products with significant enantiomeric enrichment for some of them. This extremely simple bio-catalytic approach is very useful for creating new S-C and Si-C bonds in aqueous media and may serve as the starting point for the directed evolution of artificial enzymes for such purposes.

本文展示了两种概念上不同的对映选择性激活 SH 和 Si-H 键的方法，即使用蛋白质缀合的铁络合物催化类胡萝卜素与外消旋硫醇或非手性硅烷的反应，形成对映体富集的产物。检查的催化剂是天然肌红蛋白和转铁蛋白以及血清白蛋白与适当设计的铁(III)咔咯自发形成的缀合物。在所有情况下，反应进行得非常快，并导致其中一些产物具有显着的对映体富集。这种极其简单的生物催化方法对于在水介质中创建新的 SC 和 Si-C 键非常有用，并且可以作为用于此类目的的人工酶定向进化的起点。