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

Nature Catalysis volume 2, pages 504–513 (2019)Cite this article

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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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Fig. 1: Rational design and synthesis of 1,1′-(ethene-1,1-diyl)binaphthyl.
Fig. 2: Preparative synthesis and transformation of EBINOL 7a.
Fig. 3: Application of EBINOL 7a derivatives in asymmetric catalysis.
Fig. 4: DFT calculations for the formation of 7a.

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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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Author notes

  1. These authors contributed equally: Yong-Bin Wang, Peiyuan Yu, Zhi-Peng Zhou.

Authors and Affiliations

  1. Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen, China

    Yong-Bin Wang, Zhi-Peng Zhou, Jian Zhang, Jun (Joelle) Wang, Shi-Hui Luo, Qiang-Shuai Gu & Bin Tan

  2. Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, USA

    Peiyuan Yu & K. N. Houk

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Contributions

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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Correspondence to K. N. Houk or Bin Tan.

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Supplementary information

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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