Rational design, enantioselective synthesis and catalytic applications of axially chiral EBINOLs

Yong-Bin Wang, Peiyuan Yu, Zhi-Peng Zhou, Jian Zhang, Jun (Joelle) Wang, Shi-Hui Luo, Qiang-Shuai Gu, K. N. Houk, Bin Tan

Research output: Contribution to journalArticlepeer-review

Abstract

Axially chiral 1,1′-binaphthols (BINOLs) and 1,1′-spirobiindanes (SPINOLs) have achieved great success in the field of asymmetric catalysis. Although several modifications of these skeletons have been reported, new useful scaffolds are in high demand for asymmetric catalysis. Here, on the basis of our ongoing research on atropisomeric alkenes, we have rationally designed a versatile disubstituted 1,1′-(ethene-1,1-diyl)binaphthol (EBINOL) scaffold, which would be a fine complement to 1,1′-binaphthyl and 1,1′-spirobiindane skeletons for asymmetric catalysis. To construct this axially chiral motif asymmetrically, a chiral phosphoric acid-catalysed asymmetric hydroarylation of alkynes has been developed. This approach features an efficient and convergent route to the synthesis of EBINOLs with high functional group tolerance, complete E/Z-selectivity, and excellent enantioselectivities. Density function theory calculations reveal the mechanism and provide insights into the origins of the stereoselectivity and E/Z-selectivity of this chiral Brønsted acid-catalysed alkyne activation method. The potent application of this structural scaffold is demonstrated by a series of asymmetric reactions catalysed by EBINOL derivatives.
Original languageEnglish
Pages (from-to)504–513
Number of pages10
JournalNature Catalysis
Volume2
Issue number6
DOIs
Publication statusPublished - Jun 2019

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