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From an α‐Functionalized Silicon‐Stereogenic N,O‐Silane to a Monomeric and Tetracoordinate t BuLi Adduct with Lithium‐Centered Chirality
Author(s) -
Bauer Jonathan O.,
Strohmann Carsten
Publication year - 2014
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.201404255
Subject(s) - stereocenter , silane , tetracoordinate , chirality (physics) , silanes , chemistry , deprotonation , silicon , nucleophile , stereospecificity , stereochemistry , enantioselective synthesis , organic chemistry , catalysis , ion , chiral symmetry breaking , physics , computer graphics (images) , quantum mechanics , quark , computer science , nambu–jona lasinio model , planar
Abstract Donor‐functionalized silanes with stereogenic silicon centers are extremely rare. A convenient stereocontrolled route to a nitrogen‐oxygen‐functionalized silicon‐chiral compound with an additional aminomethyl function is presented. This silane was directly achieved in stereochemically pure form by a simple nucleophilic substitution reaction. Owing to the unique asymmetry of this silane and the presence of three donor functions, the first monomeric butyllithium compound with lithium‐centered chirality could be isolated; the configuration was assigned by X‐ray crystallography. This [silane⋅ t BuLi] complex undergoes an unexpected deprotonation/stereospecific substitution sequence in toluene, leading to the development of a convenient one‐pot synthesis of a functionalized silicon‐chiral benzylsilane, which proceeds with inversion of configuration and complete preservation of the stereochemical integrity at silicon.