Phosphoramidite-based photoresponsive ligands displaying multifold transfer of chirality in dynamic enantioselective metal catalysis

ABSTRACT The transfer and amplification of chirality in biological and artificial systems is a fundamental process that allows for a dynamic control of structure and function. Only a few

responsive systems harness the dynamic transfer of chirality and can act as photoswitchable chiral inductors. Here we demonstrate that photoresponsive phosphoramidite ligands based on a

chiral biaryl-substituted molecular switch can be used to alter the activity and invert the stereoselectivity of a copper-catalysed asymmetric conjugate addition. The phosphoramidites were

obtained as pairs of diastereoisomers, each displaying a distinct catalytic activity and stereoselectivity as a result of the light-controlled matched–mismatched interaction between the

fixed chirality at the phosphorus atom and the dynamic chirality of the switch. The result is an elegant balance of two competing catalysts, of which the complementary catalytic performance

is tunable via light, which takes advantage of the internal dynamic transfer of chirality on reversible alkene photoisomerization. This discovery paves the way for the future development of

more complex chirality-dependent photoresponsive and multitasking catalysts. Access through your institution Buy or subscribe This is a preview of subscription content, access via your

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institutional subscriptions * Read our FAQs * Contact customer support SIMILAR CONTENT BEING VIEWED BY OTHERS ENANTIODIVERGENT EPOXIDATION OF ALKENES WITH A PHOTOSWITCHABLE PHOSPHATE

MANGANESE-SALEN COMPLEX Article 22 September 2022 CHIRAL BRØNSTED ACID-CONTROLLED INTERMOLECULAR ASYMMETRIC [2 + 2] PHOTOCYCLOADDITIONS Article Open access 30 September 2021 PORPHYRIN AS A

VERSATILE VISIBLE-LIGHT-ACTIVATABLE ORGANIC/METAL HYBRID PHOTOREMOVABLE PROTECTING GROUP Article Open access 24 June 2022 DATA AVAILABILITY All the data generated or analysed during this

study are included in this article (and its Supplementary Information files). Crystallographic data for the structure L1 reported has been deposited at the Cambridge Crystallographic Data

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references ACKNOWLEDGEMENTS This work was supported financially by the Netherlands Organization for Scientific Research (NWO-CW), Foundation for Fundamental Research on Matter (FOM, a

subsidiary of NWO), the Zernike Institute for Advanced Materials, The Royal Netherlands Academy of Arts and Sciences (KNAW), The European Research Council (Advanced Investigator Grant no.

694345 to B.L.F.), Ministry of Education, Culture and Science (Gravitation program 024.001.035) and the University of Groningen. The authors thank E. Otten for the X-ray structure

experiments. AUTHOR INFORMATION Author notes * These authors contributed equally: Stefano F. Pizzolato and Peter Štacko. AUTHORS AND AFFILIATIONS * Centre for Systems Chemistry, Stratingh

Institute for Chemistry and Zernike Institute for Advanced Materials, Faculty of Mathematics and Natural Sciences, University of Groningen, AG Groningen, the Netherlands Stefano F.

Pizzolato, Peter Štacko, Jos C. M. Kistemaker, Thomas van Leeuwen & Ben L. Feringa Authors * Stefano F. Pizzolato View author publications You can also search for this author inPubMed 

Google Scholar * Peter Štacko View author publications You can also search for this author inPubMed Google Scholar * Jos C. M. Kistemaker View author publications You can also search for

this author inPubMed Google Scholar * Thomas van Leeuwen View author publications You can also search for this author inPubMed Google Scholar * Ben L. Feringa View author publications You

can also search for this author inPubMed Google Scholar CONTRIBUTIONS S.F.P., P.S., J.C.M.K. and B.L.F. conceived the project. S.F.P. and P.S. carried out the experimental work. J.C.M.K. and

T.v.L. conducted the computational study. All the authors contributed to the design of the experiments, the analysis of the data and the writing of the paper. CORRESPONDING AUTHOR

Correspondence to Ben L. Feringa. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing interests. ADDITIONAL INFORMATION PUBLISHER’S NOTE Springer Nature remains neutral

with regard to jurisdictional claims in published maps and institutional affiliations. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary Methods, Figs. 1–18 and Tables 1 and

2. COMPUTATIONAL DATA 1 Cartesian coordinates. SUPPLEMENTARY DATA Crystallographic data for compound L1. RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE

Pizzolato, S.F., Štacko, P., Kistemaker, J.C.M. _et al._ Phosphoramidite-based photoresponsive ligands displaying multifold transfer of chirality in dynamic enantioselective metal catalysis.

_Nat Catal_ 3, 488–496 (2020). https://doi.org/10.1038/s41929-020-0452-y Download citation * Received: 21 October 2019 * Accepted: 13 March 2020 * Published: 04 May 2020 * Issue Date: June

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