Tuning the Chiral Environment of C₂-Symmetric Diene Ligands: Development of 3,7-Disubstituted Bicyclo[3.3.1]nona-2,6-dienes

Ryo Shintani*, Yoshitaka Ichikawa, Keishi Takatsu, Fu-Xue Chen and Tamio Hayashi*

*Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan, Email: shintanikuchem.kyoto-u.ac.jp, thayashikuchem.kyoto-u.ac.jp

R. Shintani, Y. Ichikawa, K. Takatsu, F.-X. Chen, T. Hayashi, J. Org. Chem., 2009, 74, 869-873.

DOI: 10.1021/jo802437h

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Abstract

C₂-symmetric chiral diene ligands based on a 3,7-disubstituted bicyclo[3.3.1]nona-2,6-diene readily bind to rhodium(I). These rhodium complexes act as effective catalysts for 1,4-addition of alkenyl- and arylboronic acids to various α,β-unsaturated ketones, including several combinations that were previously difficult to provide high enantioselectivity.

see article for more examples

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Simple Chiral Diene Ligands Provide High Enantioselectivities in Transition-Metal-Catalyzed Conjugate Addition Reactions

K. Okamoto, T. Hayashi, V. H. Rawal, Org. Lett., 2008, 10, 4387-4389.

Carbon-Carbon Bond-Forming Enantioselective Synthesis of Chiral Organosilicon Compounds by Rhodium/Chiral Diene-Catalyzed Asymmetric 1,4-Addition Reaction

R. Shintani, K. Okamoto, T. Hayashi, Org. Lett., 2005, 7, 4757-4759.

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Key Words

1,4-additions, vinylation

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ID: J42-Y2009-0260