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On the Mechanism of the Reductive Metallation of Asymmetrically Substituted Silyl Chlorides
Author(s) -
Oestreich Martin,
Auer Gertrud,
Keller Manfred
Publication year - 2005
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200400622
Subject(s) - silylation , chemistry , steric effects , chloride , walden inversion , medicinal chemistry , chirality (physics) , silicon , reductive elimination , stereochemistry , catalysis , organic chemistry , quark , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics
An investigation of the stereochemical course of the reductive metallation of silyl chlorides with silicon‐centred chirality has revealed two major events which are detrimental to stereoselection during silyl anion formation: (1) chloride‐induced racemisation of silyl chlorides and (2) nonstereoselective formal dimerisation during metallation providing the corresponding disilane. In control experiments, the stereochemical course of these processes has been independently verified for the reductive metallation of the enantioenriched cyclic silyl chloride (Si S )‐ 7a (R = H, er ⩾ 88:12). A screening of several related derivatives of (Si S )‐ 7a led to the sterically encumbered silyl chloride (Si R )‐ 7c (R = i Pr, er ⩾ 94:6) which displays some unique features. This structural modification prevents racemisation by lithium chloride ( T < −40 °C) as well as dimerisation ( T < −100 °C) thus allowing for the first generation of an asymmetrically substituted silyl anion (Si S )‐ 8c ( er = 74:26) by reductive metallation of a silyl chloride with silicon‐centred chirality. Moreover, the enantiospecificity of the preparation of (Si R )‐ 7c by chlorination [(Si S )‐ 9c → (Si R )‐ 7c ] and its reduction with aluminium hydrides [(Si R )‐ 7c → (Si R )‐ 9c ] have been unambiguously determined by X‐ray crystallography as retention (⩾99%) and inversion (⩾99%), respectively. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)