Terpene cyclization catalysed inside a self-assembled cavity

ABSTRACT In nature, complex terpene natural products are formed by the so-called tail-to-head terpene (THT) cyclization. The cationic reaction cascade is promoted efficiently in complex

enzyme pockets, in which cationic intermediates and transition states are stabilized. In solution, the reaction is hard to control and man-made catalysts able to perform selective THT

cyclizations are lacking. We herein report the first example of a successful THT cyclization inside a supramolecular structure. The basic mode of operation in cyclase enzymes was mimicked

successfully and a catalytic non-stop THT was achieved with geranyl acetate as the substrate. The results presented have implications for the postulated reaction mechanism in cyclase

enzymes. Evidence indicates that the direct isomerization of a geranyl cation to the _cisoid_ isomer, which so far was considered unlikely, is feasible. Access through your institution Buy

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OTHERS ENZYME-LIKE POLYENE CYCLIZATIONS CATALYZED BY DYNAMIC, SELF-ASSEMBLED, SUPRAMOLECULAR FLUORO ALCOHOL-AMINE CLUSTERS Article Open access 13 February 2023 BIOCATALYTIC STEREOCONTROLLED

HEAD-TO-TAIL CYCLIZATIONS OF UNBIASED TERPENES AS A TOOL IN CHEMOENZYMATIC SYNTHESIS Article Open access 10 June 2024 A MONODOMAIN CLASS II TERPENE CYCLASE ASSEMBLES COMPLEX ISOPRENOID

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104, 1422–1424 (1982). Article  CAS  Google Scholar  Download references ACKNOWLEDGEMENTS This project was supported by the Bayerischen Akademie der Wissenschaften (Junges Kolleg), Fonds der

Chemischen Industrie (Sachkostenzuschuss), the TUM Junior Fellow Fund and the Dr.-Ing. Leonhard-Lorenz-Stiftung. The help of J. Richers with the graphical design is gratefully acknowledged.

AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * Department Chemie, Technische Universität München, Lichtenbergstraße 4, Garching, D-85747, Germany Q. Zhang & K. Tiefenbacher Authors * Q.

Zhang View author publications You can also search for this author inPubMed Google Scholar * K. Tiefenbacher View author publications You can also search for this author inPubMed Google

Scholar CONTRIBUTIONS K.T. conceived the project and wrote the manuscript with Q.Z. Q.Z. planned and carried out the experiments. K.T. and Q.Z. discussed the experiments and results.

CORRESPONDING AUTHOR Correspondence to K. Tiefenbacher. ETHICS DECLARATIONS COMPETING INTERESTS The authors declare no competing financial interests. SUPPLEMENTARY INFORMATION SUPPLEMENTARY

INFORMATION Supplementary information (PDF 5155 kb) RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Zhang, Q., Tiefenbacher, K. Terpene cyclization

catalysed inside a self-assembled cavity. _Nature Chem_ 7, 197–202 (2015). https://doi.org/10.1038/nchem.2181 Download citation * Received: 15 September 2014 * Accepted: 12 January 2015 *

Published: 16 February 2015 * Issue Date: March 2015 * DOI: https://doi.org/10.1038/nchem.2181 SHARE THIS ARTICLE Anyone you share the following link with will be able to read this content:

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