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Chiral Dilithiomethane Derivatives: Structure Determination and Application in Stereoselective Reactions
Author(s) -
Müller Jürgen F. K.
Publication year - 2000
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(200005)2000:5<789::aid-ejic789>3.0.co;2-s
Subject(s) - chemistry , stereoselectivity , transmetalation , electrophile , reagent , alkylation , aldehyde , computational chemistry , combinatorial chemistry , organic chemistry , catalysis
The synthesis and X‐ray analysis of chiral dilithiomethane analogues derived from sulfoximines are presented. The structures of the sulfoximine‐stabilised mono‐ and dilithio salts have been compared and allow a rationalization of the second lithiation. Organophosphorus‐based dilithiomethane derivatives are also structurally described. The gas‐phase structures of N , S , S ‐trimethylsulfoximine 19 and of its mono‐ and dilithiated isomers 20–21 were calculated by ab initio methods employing different levels of theory. For an application in asymmetric synthesis, the dilithiation of ( N ‐methyl)‐ S ‐ethyl‐ S ‐phenylsulfoximine ( 11 ) afforded a chiral dinucleophile that undergoes highly regio‐ and stereoselective alkylation reactions with electrophiles. The transmetallation of a chiral dilithiomethane reagent such as 14 with ClTi(O i Pr) 3 followed by addition of an aldehyde, constitutes a simple one‐pot process for the formation of ( E )‐alkenylsulfoximines with excellent diastereoselectivity.