Expanding the C2-Symmetric Bicyclo[2.2.1]hepta-2,5-diene Ligand Family: Concise Synthesis and Catalytic Activity in Rhodium-Catalyzed Asymmetric Addition
- 10 October 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 71 (23), 8957-8960
- https://doi.org/10.1021/jo061385s
Abstract
New C2-symmetric bicyclo[2.2.1]hepta-2,5-dienes bearing methyl and phenyl substituents at the 2 and 5 positions were prepared enantiomerically pure through a two-step sequence starting from the readily available bicyclo[2.2.1]hepta-2,5-dione. Due to the instability or volatility of these dienes, their isolation was achieved through the formation of the corresponding stable [RhCl(diene)]2 complexes. These chiral rhodium complexes displayed high activity and enantioselectivity (up to 99% ee) in the rhodium-catalyzed 1,4-addition and 1,2-addition of phenylboronic acid to cyclic enones and N-sulfonylimines, respectively.Keywords
This publication has 36 references indexed in Scilit:
- Asymmetric 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Aldehydes Catalyzed by a Chiral Diene–Rhodium ComplexChemistry Letters, 2005
- Asymmetric Synthesis of 3,3-Diarylpropanals with Chiral Diene−Rhodium CatalystsJournal of the American Chemical Society, 2005
- Highly Chemo‐ and Enantioselective Arylative Cyclization of Alkyne‐Tethered Electron‐Deficient Olefins Catalyzed by Rhodium Complexes with Chiral DienesAngewandte Chemie International Edition, 2005
- Rhodium/diene-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated Weinreb amidesChemical Communications, 2005
- Rational Design of a Chiral Palladium(0) Olefin Complex of Unprecedented StabilityOrganometallics, 2005
- Chiral Olefins as Steering Ligands: Syntheses of C1-Symmetric Dibenzo[a,e]cyclooctenes (Rdbcot)Organometallics, 2005
- Preparation of C2-Symmetric Bicyclo[2.2.2]octa-2,5-diene Ligands and Their Use for Rhodium-Catalyzed Asymmetric 1,4-Addition of Arylboronic AcidsThe Journal of Organic Chemistry, 2005
- Enantioselective Synthesis of DIANANE, a Novel C2-Symmetric Chiral Diamine for Asymmetric CatalysisThe Journal of Organic Chemistry, 2004
- Highly Stereo- and Chemoselective Iron-Catalyzed Alkenylation of Organomagnesium CompoundsSynthesis, 1998
- Activation of Grignard reagents by transition-metal complexes. A new and simple synthesis of trans-stilbenes and polyphenylsJournal of the Chemical Society, Chemical Communications, 1972