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Modification of chiral dimethyl tartrate through transesterification: Immobilization on POSS and enantioselectivity reversal in sharpless asymmetric epoxidation
Author(s) -
García Rafael A.,
Van Grieken Rafael,
Iglesias José,
Sherrington David C.,
Gibson Colin L.
Publication year - 2010
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.20814
Subject(s) - chemistry , tartrate , enantioselective synthesis , ligand (biochemistry) , silsesquioxane , enantiomer , organic chemistry , allylic rearrangement , transesterification , chiral ligand , catalysis , polymer , biochemistry , receptor
Abstract Modification of dimethyl tartrate has been investigated through transesterification with aminoalcohols to provide reactive functionalities for the covalent bonding of chiral tartrate to polyhedral oligomeric silsesquioxanes. The transesterification of dimethyl tartrate has been widely studied using different catalytic systems and reaction conditions. Through the proper selection of both the catalytic system and the reaction conditions, it is possible to achieve monosubstituted or bis‐substituted tartrate derivatives as sole products. All the intermediate chiral tartrate‐derived ligands were successfully used in the homogeneous enantioselective epoxidation of allylic alcohols providing moderate enantiomeric excess over the products. Attached amine groups have been used to support the modified tartrate ligands on to a haloaryl‐functionalized silsesquioxane moiety. This final chiral tartrate ligand displays reverse enantioselectivity in the asymmetric epoxidation of allylic alcohols with regard to the starting dimethyl tartrate ligand, both molecules having the same chiral sign. However, the POSS‐containing ligand can be easily recovered in almost quantitative yield and reused in asymmetric epoxidation reactions. In addition, recovered silsesquioxane‐pendant ligand, though displaying decreasing catalytic activity in recycling epoxidation tests, showed very stable enantioselective behavior. Chirality 2010. © 2009 Wiley‐Liss, Inc.