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Stereoselective Synthesis and Reactions of Secondary Alkyllithium Reagents Functionalized at the 3‐Position
Author(s) -
Moriya Kohei,
Didier Dorian,
Simon Meike,
Hammann Jeffrey M.,
Berionni Guillaume,
Karaghiosoff Konstantin,
Zipse Hendrik,
Mayr Herbert,
Knochel Paul
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201409165
Subject(s) - electrophile , chemistry , reagent , stereoselectivity , diastereomer , alkyl , lithium (medication) , yield (engineering) , epimer , carbon atom , medicinal chemistry , electrophilic substitution , combinatorial chemistry , organic chemistry , catalysis , medicine , materials science , metallurgy , endocrinology
Secondary alkyllithium reagents bearing an OTBS group (TBS= tert ‐butyldimethylsilyl) at the 3‐position can be prepared stereoconvergently through an I/Li exchange from a diastereomeric mixture of the corresponding secondary alkyl iodides. These lithium reagents react with a range of electrophiles, including carbon electrophiles, with retention of configuration to yield various 1,3‐difunctionalized derivatives with good diastereoselectivities. Kinetic studies show that the 3‐siloxy group strongly accelerates the epimerization at the lithium‐substituted carbon atom. This method offers a new way to construct chiral open‐chain molecules with excellent stereoselectivity.