Some unusual transformations of a highly reactive α-bromocaranone
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.
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.Attached Files
Supplemental Material - 1-s2.0-S004040392100784X-mmc1.zip
Supplemental Material - 1-s2.0-S004040392100784X-mmc10.zip
Supplemental Material - 1-s2.0-S004040392100784X-mmc11.zip
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Supplemental Material - 1-s2.0-S004040392100784X-mmc13.pdf
Supplemental Material - 1-s2.0-S004040392100784X-mmc14.xlsx
Supplemental Material - 1-s2.0-S004040392100784X-mmc2.zip
Supplemental Material - 1-s2.0-S004040392100784X-mmc3.zip
Supplemental Material - 1-s2.0-S004040392100784X-mmc4.zip
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Supplemental Material - 1-s2.0-S004040392100784X-mmc6.zip
Supplemental Material - 1-s2.0-S004040392100784X-mmc7.zip
Supplemental Material - 1-s2.0-S004040392100784X-mmc8.zip
Supplemental Material - 1-s2.0-S004040392100784X-mmc9.zip
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Additional details
- Eprint ID
- 112847
- DOI
- 10.1016/j.tetlet.2021.153496
- Resolver ID
- CaltechAUTHORS:20220112-698034937
- NSF
- CHE-1800511
- NSF Graduate Research Fellowship
- DOW Next Generation Instrument Fund
- Created
-
2022-01-12Created from EPrint's datestamp field
- Updated
-
2022-01-12Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute