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Catalytic enantioselective organozinc addition toward optically active tertiary alcohol synthesis
Article first published online: 18 JUN 2008
DOI: 10.1002/tcr.20146
© 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.
1528-0691/asset/cover.gif?v=1&s=0a54cc887bcc8e5a84864699938fe84d8b67adb8 "The Chemical Record")
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How to Cite
Hatano, M. and Ishihara, K. (2008), Catalytic enantioselective organozinc addition toward optically active tertiary alcohol synthesis. Chem Record, 8: 143–155. doi: 10.1002/tcr.20146
Publication History
- Issue published online: 18 JUN 2008
- Article first published online: 18 JUN 2008
- Manuscript Accepted: 6 MAR 2008
- Manuscript Received: 14 FEB 2008
- Abstract
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Keywords:
- alcohol;
- asymmetric catalysis;
- Lewis acid–Lewis base catalyst;
- organometallics;
- zinc(II)
Abstract
A highly enantioselective organozinc (R2Zn) addition to a series of aldehydes and ketones was developed based on conjugate Lewis acid–Lewis base catalysis. Optically active secondary and tertiary alcohols were obtained in high yields with high enantioselectivities without Ti(IV) compounds. Bifunctional chiral 3,3′-diphosphoryl-BINOL ligands were designed and prepared through a phospho-Fries rearrangement as a key step. On the other hand, bifunctional chiral phosphoramide ligands were designed and prepared from L-valine. Mechanistic studies were performed by X-ray analyses of Zn(II) cluster and chiral ligands, a 31P NMR experiment on Zn(II) complexes, and stoichiometric reactions with some chiral or achiral Zn(II) complexes to propose a transition state assembly that includes monomeric active intermediates. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 143–155; 2008: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20146