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Enantioselective Additions of Aryltitanium Tris(isopropoxide) to Ketones: Structure of [(i-PrO)2Ti{μ-(S)-BINOLate}(μ-O-i-Pr)TiPh(O-i-Pr)2], Study of Mechanistic and Stereochemical Insights

  1. Kuo-Hui Wu,
  2. Yi-Yin Kuo,
  3. Chien-An Chen,
  4. Yi-Ling Huang,
  5. Han-Mou Gau*

Article first published online: 28 FEB 2013

DOI: 10.1002/adsc.201200672

Issue

Advanced Synthesis & Catalysis

Advanced Synthesis & Catalysis

Volume 355, Issue 5, pages 1001–1008, March 25, 2013

Additional Information

How to Cite

Wu, K.-H., Kuo, Y.-Y., Chen, C.-A., Huang, Y.-L. and Gau, H.-M. (2013), Enantioselective Additions of Aryltitanium Tris(isopropoxide) to Ketones: Structure of [(i-PrO)2Ti{μ-(S)-BINOLate}(μ-O-i-Pr)TiPh(O-i-Pr)2], Study of Mechanistic and Stereochemical Insights. Adv. Synth. Catal., 355: 1001–1008. doi: 10.1002/adsc.201200672

Author Information

  1. Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan, ROC, Fax: (+886)-4-2286-2547

*Department of Chemistry, National Chung Hsing University, Taichung 402, Taiwan, ROC, Fax: (+886)-4-2286-2547

Publication History

  1. Issue published online: 25 MAR 2013
  2. Article first published online: 28 FEB 2013
  3. Manuscript Revised: 22 NOV 2012
  4. Manuscript Received: 31 JUL 2012

Funded by

  • National Science Council of Taiwan. Grant Number: number of NSC 99-2113M-005-005-MY3

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Keywords:

  • aryl addition;
  • aryltitaniums;
  • enantioselectivity;
  • ketones;
  • titanium

Abstract

Aryl addition reactions of ArTi(O-i-Pr)3 to aromatic, heteroaromatic, or α,β-unsaturated ketones are described, producing tertiary alcohols in good to excellent enantioselectivities of up to 97% ee. The structure of the dititanium complex [(i-PrO)2Ti{μ-(S)-BINOLate}(μ-O-i-Pr)TiPh(O-i-Pr)2] [(S)-4] that simultaneously bears a chiral directing ligand and a nucleophile is reported. Complex (S)-4 possesses a pocket structure and has been illustrated as the key active species for addition reactions of both aldehydes and ketones. Mechanistic and stereochemical insights concerning addition reactions of organometallic reagents to organic carbonyls are rationalized based on the pocket structure and pocket size of (S)-4.

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