期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 16, 页码 5202-5205出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b01458
关键词
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资金
- National Natural Science Foundation of China [81373303, 81473080, 81573299, 21502230]
- Jiangsu Province Natural Science Foundation [BK20150688]
- Program for Changjiang Scholars and Innovative Research Team in University [IRT1193]
- Rice University
- NIH [R01 GM-114609-01]
- NSF [CAREER:-SusChEM CHE-1455335]
- Robert A. Welch Foundation [C-1764]
- ACS-PRF [51707-DNI1]
- Amgen
- Biotage
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1546097] Funding Source: National Science Foundation
Herein we disclose a scalable organo-catalytic direct arylation approach for the regio- and atroposelective synthesis of non-C-2-symmetric 2,2'-diliydroxy-1,1'-binaphthalenes (BINOLs). In the presence of catalytic amounts of axially chiral phosphoric acids, phenols and naphthols are coupled with iminoquinones via a cascade process that involves sequential aminal formation, sigmatropic rearrangement, and rearomatization to afford enantiomerically enriched BINOL derivatives in good to excellent yields. Our studies suggest that the (local) symmetry of the initially formed aminal intermediate has a dramatic impact on the level of enantioinduction in the final product. Aminals with a plane of symmetry give rise to BINOL derivatives with significantly lower enantiomeric excess than unsymmetrical ones featuring a stereogenic center. Presumably asymmetric induction in the sigmatropic rearrangement step is significantly more challenging than during aminal formation. Sigmatropic rearrangement of the enantiomerically enriched aminal and subsequent rearomatization transfers the central chirality into axial chirality with high fidelity.
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