Construction of axial chirality via palladium/chiral norbornene cooperative catalysis

ABSTRACT Axially chiral biaryls are common structural motifs in functional materials, bioactive natural products, pharmaceuticals and chiral catalysts/ligands. As such, efficient preparation

of these privileged scaffolds is an important endeavour in organic chemistry. Herein we report a general and modular platform technology for the construction of axial chirality via

palladium/chiral norbornene cooperative catalysis. It is a three-component cascade process that involves widely available aryl iodides, 2,6-substituted aryl bromides and olefins (or alkynes,

boronic acids and so on) as the reactants. A wide variety of substrates bearing an assortment of functional groups (88 examples) are compatible with this method. Other features include a

distinct stereoinduction model, excellent enantioselectivities, step economy and scalability. This method is also amenable for the synthesis of chiral fluorenols through axial-to-central

chirality transfer in high stereochemical fidelity. We anticipate that this work will have broad synthetic utilities in chiral ligands and catalyst-design for asymmetric catalysis. Access

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VIEWED BY OTHERS BIS-INDOLE CHIRAL ARCHITECTURES FOR ASYMMETRIC CATALYSIS Article Open access 17 April 2025 CHIRAL DINITROGEN LIGAND ENABLED ASYMMETRIC PD/NORBORNENE COOPERATIVE CATALYSIS

TOWARD THE ASSEMBLY OF C–N AXIALLY CHIRAL SCAFFOLDS Article Open access 08 June 2024 CATALYTIC ATROPOSELECTIVE SYNTHESIS OF AXIALLY CHIRAL BENZONITRILES VIA CHIRALITY CONTROL DURING BOND

DISSOCIATION AND CN GROUP FORMATION Article Open access 10 January 2022 DATA AVAILABILITY Data relating to the materials, optimization studies, experimental procedures and characterization

of the new compounds are available in the Supplementary Information. Crystallographic data for 4g, 4da and 5j are available free of charge from the Cambridge Crystallographic Database Centre

(CCDC) under reference numbers 1946138, 1946094 and 1946139, respectively. All other data are available from the authors on reasonable request. REFERENCES * Kumarasamy, E., Raghunathan, R.,

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Download references ACKNOWLEDGEMENTS We are grateful to the National Natural Science Foundation of China (grant nos. 21871213 and 21801193), the China Postdoctoral Science Foundation (grant

nos. 2016M602339 and 2018M642894) and the start-up funding from WHU for financial support. We thank H. Cong and W. Yan (Wuhan University) for X-ray crystallographic analysis assistance. We

gratefully acknowledge P. Baran (TSRI), D. Ma and W. Tang (SIOC), H. Xu (Georgia State University), C. Wang and W.-B. Liu (Wuhan University), S. Yu (Nanjing University) and W. Xie (Northwest

A&F University) for helpful discussions, H. Xu (Georgia State University) and M. Yan (Fish & Richardson) for help with preparation of the manuscript. AUTHOR INFORMATION Author notes

* These authors contributed equally: Yu Hua and Qianwen Gao. AUTHORS AND AFFILIATIONS * Sauvage Center for Molecular Sciences, Engineering Research Center of Organosilicon Compounds &

Materials (Ministry of Education), College of Chemistry and Molecular Sciences and The Institute for Advanced Studies, Wuhan University, Wuhan, P. R. China Ze-Shui Liu, Yu Hua, Qianwen Gao, 

Yuanyuan Ma, Hua Tang, Yong Shang, Hong-Gang Cheng & Qianghui Zhou Authors * Ze-Shui Liu View author publications You can also search for this author inPubMed Google Scholar * Yu Hua

View author publications You can also search for this author inPubMed Google Scholar * Qianwen Gao View author publications You can also search for this author inPubMed Google Scholar *

Yuanyuan Ma View author publications You can also search for this author inPubMed Google Scholar * Hua Tang View author publications You can also search for this author inPubMed Google

Scholar * Yong Shang View author publications You can also search for this author inPubMed Google Scholar * Hong-Gang Cheng View author publications You can also search for this author

inPubMed Google Scholar * Qianghui Zhou View author publications You can also search for this author inPubMed Google Scholar CONTRIBUTIONS Q.Z. and Z.-S.L. conceived the idea. Q.Z. guided

the project and wrote the manuscript. Z.-S.L., Y.H., Q.G., Y.M., H.T. and Y.S. performed the experiments and analysed the data. Z.-S.L. and H.-G.C. participated in the preparation of the

manuscript. CORRESPONDING AUTHOR Correspondence to Qianghui Zhou. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. ADDITIONAL INFORMATION PUBLISHER’S NOTE

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Methods, Figs. 1–11, Tables 1–17 and references. SUPPLEMENTARY DATA 1 Crystallographic Data of compound 4da. SUPPLEMENTARY DATA 2 Crystallographic Data of compound 4g. SUPPLEMENTARY DATA 3

Crystallographic Data of compound 5j. RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Liu, ZS., Hua, Y., Gao, Q. _et al._ Construction of axial chirality

via palladium/chiral norbornene cooperative catalysis. _Nat Catal_ 3, 727–733 (2020). https://doi.org/10.1038/s41929-020-0494-1 Download citation * Received: 28 February 2020 * Accepted: 08

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