Grünenfelder, Denise C. and Navarro, Raul and Wang, Haoxuan and Fastuca, Nicholas J. and Butler, John R. and Reisman, Sarah E. (2022) Enantioselective Synthesis of (−)-10-Hydroxyacutuminine. Angewandte Chemie International Edition, 61 (16). Art. No. e202117480. ISSN 1433-7851. doi:10.1002/anie.202117480. https://resolver.caltech.edu/CaltechAUTHORS:20220204-679540000
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Abstract
An enantioselective synthesis of (−)-10-hydroxyacutuminine is reported. Central to our strategy is a photochemical [2+2] cycloaddition that forges two of the quaternary stereocenters present in the acutumine alkaloids. A subsequent retro-aldol/Dieckmann sequence furnishes the spirocyclic cyclopentenone. Efforts to chlorinate the acutumine scaffold at C10 under heterolytic or radical deoxychlorination conditions led to the synthesis of an unexpected cyclopropane-containing pentacycle.
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| Alternate Title: | Enantioselective Synthesis of (-)-C10-Hydroxyacutuminine | ||||||||
| Additional Information: | © 2022 Wiley-VCH. Issue Online: 03 April 2022; Version of Record online: 23 February 2022; Accepted manuscript online: 02 February 2022; Manuscript received: 22 December 2021. We are grateful to Dr. Scott Virgil and the Caltech Center for Catalysis and Chemical Synthesis for access to analytical equipment, and Dr. David VanderVelde for assistance with NMR structural analysis. Dr. Lawrence M. Henling is acknowledged for the acquisition, and Dr. Michael K. Takase and Dr. Julie L. Hofstra for solving the X-ray crystal structure of 34. We also thank Dr. Nicholas G. W. Cowper, Dr. Elliot P. Farney, and Dr. Jordan C. Beck for helpful discussions, and Yujia Tao for the synthesis and characterization of ketone 24, as well as assistance in the chlorination trials of cyclopropane 35. Financial support was provided by the National Science Foundation (graduate research fellowship to D. C. G., Grant No. DGE-1144469, and CAREER-1057143, CHE-1800536 to S. E. R.) and is gratefully acknowledged. The authors declare no conflict of interest. Data Availability Statement: The data that support the findings of this study are available in the supplementary material of this article. | ||||||||
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| Subject Keywords: | Acutumine Alkaloids; Deoxychlorination; Dieckmann Cyclization; Total Synthesis; [2+2] Cycloaddition | ||||||||
| Issue or Number: | 16 | ||||||||
| DOI: | 10.1002/anie.202117480 | ||||||||
| Record Number: | CaltechAUTHORS:20220204-679540000 | ||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20220204-679540000 | ||||||||
| Official Citation: | Enantioselective Synthesis of (−)-10-Hydroxyacutuminine. D. C. Grünenfelder, R. Navarro, H. Wang, N. J. Fastuca, J. R. Butler, S. E. Reisman, Angew. Chem. Int. Ed. 2022, 61, e202117480; Angew. Chem. 2022, 134, e202117480. | ||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||
| ID Code: | 113284 | ||||||||
| Collection: | CaltechAUTHORS | ||||||||
| Deposited By: | George Porter | ||||||||
| Deposited On: | 07 Feb 2022 20:24 | ||||||||
| Last Modified: | 06 Apr 2022 21:37 |
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