Remarkably Diastereoselective Synthesis of a Chiral Biphenyl Diphosphine Ligand and Its Application in Asymmetric Hydrogenation

Remarkably Diastereoselective Synthesis of a Chiral Biphenyl Diphosphine Ligand and Its Application in Asymmetric Hydrogenation

Essentially complete atropdiastereoselectivity was realized in the preparation of biaryl diphosphine dioxide by asymmetric intramolecular Ullmann coupling and oxidative coupling with central-to-axial chirality transfer. A bridged C2-symmetric biphenyl phosphine ligand possessing additional chiral ce...

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Published in:Proceedings of the National Academy of Sciences - PNAS Vol. 101; no. 16; pp. 5815 - 5820
Main Authors: Qiu, Liqin, Wu, Jing, Chan, Shusun, Terry T.-L. Au-Yeung, Ji, Jian-Xin, Guo, Rongwei, Pai, Cheng-Chao, Zhou, Zhongyuan, Li, Xingshu, Fan, Qing-Hua, Albert S. C. Chan, Halpern, Jack
Format: Journal Article
Language:English
Published: United States National Academy of Sciences 20-04-2004
National Acad Sciences
Series:Asymmetric Catalysis Special Feature Part II
Subjects:
Acetates
Asymmetric Catalysis Special Feature Part II
Chirality
Dioxides
Hydrogenation
Ligands
Lithium
Organic chemistry
Phosphines
Physical Sciences
Room temperature
Solvents
Tetrahedrons
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Summary:Essentially complete atropdiastereoselectivity was realized in the preparation of biaryl diphosphine dioxide by asymmetric intramolecular Ullmann coupling and oxidative coupling with central-to-axial chirality transfer. A bridged C2-symmetric biphenyl phosphine ligand possessing additional chiral centers on the linking unit of the biphenyl groups was synthesized. No resolution step was required for the preparation of the enantiomerically pure chiral ligand. These findings offer a general and practical tool for the development of previously uninvestigated atropdiastereomeric biaryl phosphine ligands. The diphosphine ligand was found to be highly effective in the asymmetric hydrogenation of α- and β- ketoesters, 2-(6′-methoxy-2′-naphthyl)propenoic acid, β-(acylamino)acrylates, and enol acetates.
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content type line 23
To whom correspondence should be addressed. E-mail: bcachan@polyu.edu.hk.
Edited by Jack Halpern, University of Chicago, Chicago, IL, and approved February 17, 2004
This paper was submitted directly (Track II) to the PNAS office.
Abbreviations: rt, room temperature; ee, enantiomeric excess; MeO-BIPHEP, 2,2′-bis(diphenylphosphino)-6,6′-dimethoxy-1,1′-biphenyl; BINAP, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl; DMF, dimethylformamide; THF, tetrahydrofuran.
ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.0307774101