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Some unusual transformations of a highly reactive α-bromocaranone

Samkian, Adrian E. and Sercel, Zachary P. and Virgil, Scott C. and Stoltz, Brian M. (2022) Some unusual transformations of a highly reactive α-bromocaranone. Tetrahedron Letters, 89 . Art. No. 153496. ISSN 0040-4039. doi:10.1016/j.tetlet.2021.153496. https://resolver.caltech.edu/CaltechAUTHORS:20220112-698034937

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Abstract

The facile synthesis of a highly reactive α-bromocaranone from (+)-carene is reported. This intermediate was found to generate diverse chiral building blocks through radical or carbocation mediated cyclopropyl fragmentation reactions in moderate to excellent yields. Furthermore, the formation of an unexpected carvone derivative prompted several control studies that provided mechanistic insight into an unusual transformation. This study not only demonstrates the synthesis of a variety of chiral building blocks but provides insight into the reactivity of keto-halo-cyclopropanes in general.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1016/j.tetlet.2021.153496DOIArticle
ORCID:
AuthorORCID
Samkian, Adrian E.0000-0002-0068-3572
Virgil, Scott C.0000-0001-8586-5641
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2021 Published by Elsevier. Received 6 September 2021, Revised 14 October 2021, Accepted 18 October 2021, Available online 22 October 2021. We gratefully acknowledge the National Science Foundation (Grant CHE-1800511) for financial support. Z.P.S. thanks the National Science Foundation for a predoctoral fellowship. The computations presented here were conducted in the Resnick High Performance Computing Center, a facility supported by Resnick Sustainability Institute at the California Institute of Technology. Chiral SFC analysis and preparatory HPLC were performed with instrumentation at the Caltech Center for Catalysis and Chemical Synthesis, a facility of the Beckman Institute at Caltech. High resolution mass spectrometry was performed on an instrument funded by DOW Next Generation Instrument Funds. We thank Alexander Q. Cusumano (Caltech) for assistance with DFT calculations as well as helpful discussions. We thank Dr. Dave VanderVelde (Caltech) for NMR expertise, and Dr. Mona Shahgoli (Caltech) for HRMS data acquisition. This manuscript is dedicated to our friend and colleague Professor Steve Martin in special recognition of his dedication to the Tetrahedron family of journals. Declaration of Competing Interest: The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Brian M. Stoltz reports financial support was provided by National Science Foundation. I, Brian M. Stoltz am Editor in Chief of Tetrahedron, the sister journal to which we are submitting.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
NSFCHE-1800511
NSF Graduate Research FellowshipUNSPECIFIED
DOW Next Generation Instrument FundUNSPECIFIED
Subject Keywords:Carene; Ring fragmentation; Chiral building blocks; Terpenes
DOI:10.1016/j.tetlet.2021.153496
Record Number:CaltechAUTHORS:20220112-698034937
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220112-698034937
Official Citation:Adrian E. Samkian, Zachary P. Sercel, Scott C. Virgil, Brian M. Stoltz, Some unusual transformations of a highly reactive α-bromocaranone, Tetrahedron Letters, Volume 89, 2022, 153496, ISSN 0040-4039, https://doi.org/10.1016/j.tetlet.2021.153496.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:112847
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:12 Jan 2022 11:40
Last Modified:12 Jan 2022 23:54

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