Mendoza, Skyler D. and Rombola, Michael and Tao, Yujia and Zuend, Stephan J. and Götz, Roland and McLaughlin, Martin J. and Reisman, Sarah E. (2022) Expanding the Chiral Monoterpene Pool: Enantioselective Diels–Alder Reactions of α-Acyloxy Enones. Organic Letters, 24 (21). pp. 3802-3806. ISSN 1523-7060. doi:10.1021/acs.orglett.2c01343. https://resolver.caltech.edu/CaltechAUTHORS:20220523-165225000
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Abstract
An enantioselective Diels–Alder (DA) reaction of α-acyloxy enones has been developed to synthesize chiral oxidized cyclohexenes. Yttrium(III) triflate, in conjunction with a chiral pyridinebisimidazoline (PyBim) ligand, was found to catalyze the asymmetric [4 + 2] cycloaddition with a variety of dienes and α-acyloxy enone dienophiles. Using this method, terpinene-4-ol, a key intermediate in the synthesis of commercial herbicide cinmethylin, can be prepared in four steps from isoprene. A combination of kinetic data and NMR studies support a mechanism involving reversible binding of a dienophile to a yttrium catalyst followed by cycloaddition with a diene as the rate-determining step.
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| Additional Information: | © 2022 American Chemical Society. Received 17 April 2022. Published online 20 May 2022. This work was financially supported by BASF (SA-9852). We thank Dr. S. Virgil (Caltech) and the Caltech Center for Catalysis and Chemical Synthesis for access to analytical equipment. Nicholas J. Fastuca (Caltech) is gratefully acknowledged for experimental help regarding kinetics experiments. Dr. Caitlin R. Lacker (Caltech) is gratefully acknowledged for discussion of the substrate scope. Author Contributions. S.D.M. and M.R. contributed equally. The authors declare the following competing financial interest(s): A patent has been filed: Reisman, S.; Rombola, M.; Ladd, C. L.; McLaughlin, M. J.; Zuend, S.; Götz, R. Process for the synthesis of non-racemic cyclohexenes. US Patent WO 2021/007141 A1, January 2021. | ||||||||||||
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| Subject Keywords: | Addition reactions, Catalysts, Cyclization, Ligands, Organic compounds | ||||||||||||
| Issue or Number: | 21 | ||||||||||||
| DOI: | 10.1021/acs.orglett.2c01343 | ||||||||||||
| Record Number: | CaltechAUTHORS:20220523-165225000 | ||||||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20220523-165225000 | ||||||||||||
| Official Citation: | Expanding the Chiral Monoterpene Pool: Enantioselective Diels–Alder Reactions of α-Acyloxy Enones. Skyler D. Mendoza, Michael Rombola, Yujia Tao, Stephan J. Zuend, Roland Götz, Martin J. McLaughlin, and Sarah E. Reisman. Organic Letters 2022 24 (21), 3802-3806; DOI: 10.1021/acs.orglett.2c01343 | ||||||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||
| ID Code: | 114886 | ||||||||||||
| Collection: | CaltechAUTHORS | ||||||||||||
| Deposited By: | George Porter | ||||||||||||
| Deposited On: | 23 May 2022 20:03 | ||||||||||||
| Last Modified: | 16 Jun 2022 17:57 |
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