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.
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Data availability
The X-ray crystallographic coordinates for structures of 5k, 7g and Phos-9a reported in this Article have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition numbers CCDC 1867697, CCDC 1867700 and CCDC 1867701, respectively. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif. Experimental procedures, characterization of all new compounds, Supplementary Tables and Supplementary Figures are available in the Supplementary Information. All of the related DFT computational data are provided in Supplementary Data 1. All other data are available from the authors upon reasonable request.
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Acknowledgements
The authors acknowledge financial support from the National Natural Science Foundation of China (grants nos. 21772081, 21825105, 21801121), Shenzhen special funds for the development of biomedicine, Internet, new energy and new material industries (JCYJ20170412151701379, KQJSCX20170328153203) and the Shenzhen Nobel Prize Scientists Laboratory Project (C17213101). P.Y. and K.N.H. acknowledge computational resources provided by the Institute of Digital Research and Education (IDRE) at UCLA and by the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the NSF (OCI-1053575).
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B.T. conceived and designed the experiments. Y.-B.W. and Z.-P.Z. performed experiments and prepared the Supplementary Information. J.Z., S.-H.L. and Q.-S.G. helped with new compounds and in analysing the data. J.W. directed the applications. P.Y. performed the DFT calculations and mechanism analysis. K.N.H. directed the DFT calculations and mechanism analysis. B.T., Y.-B.W., P.Y. and K.N.H. wrote the paper. Y.-B.W., P.Y. and Z.-P.Z contributed equally to this work. All authors discussed the results and commented on the manuscript.
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Supplementary Information
Supplementary methods, Supplementary Tables 1–7, Supplementary Figs. 1–6, Supplementary references
Supplementary Data 1
Cartesian coordinates of DFT-computed structures
Compound 5k
Crystallographic data for compound 5k
Compound 7g
Crystallographic data for compound 7g
Compound Phos-9a
Crystallographic data for compound Phos-9a
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Wang, YB., Yu, P., Zhou, ZP. et al. Rational design, enantioselective synthesis and catalytic applications of axially chiral EBINOLs. Nat Catal 2, 504–513 (2019). https://doi.org/10.1038/s41929-019-0278-7
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DOI: https://doi.org/10.1038/s41929-019-0278-7
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