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Divergent and Stereoselective Synthesis of β‐Silyl‐α‐Amino Acids through Palladium‐Catalyzed Intermolecular Silylation of Unactivated Primary and Secondary C−H Bonds
Author(s) -
Liu YueJin,
Liu YanHua,
Zhang ZhuoZhuo,
Yan ShengYi,
Chen Kai,
Shi BingFeng
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201607766
Subject(s) - silylation , chemistry , stereoselectivity , intermolecular force , catalysis , amino acid , molecule , palladium , cholic acid , combinatorial chemistry , silyl ether , stereoisomerism , organic chemistry , stereochemistry , bile acid , biochemistry
Abstract A general and practical Pd II ‐catalyzed intermolecular silylation of primary and secondary C−H bonds of α‐amino acids and simple aliphatic acids is reported. This method provides divergent and stereoselective access to a variety of optical pure β‐silyl‐α‐amino acids, which are useful for genetic technologies and proteomics. It can also be readily performed on a gram scale and the auxiliary can be easily removed with retention of configuration. The synthetic importance of this method is further demonstrated by the late‐stage functionalization of biological small molecules, such as (−)‐santonin and β‐cholic acid. Moreover, several key palladacycles were successfully isolated and characterized to elucidate the mechanism of this β−C(sp 3 )‐H silylation process.