Silicon-Carbon Bond Formation via Nickel-Catalyzed Cross-Coupling of Silicon Nucleophiles with Unactivated Secondary and Tertiary Alkyl Electrophiles
- Creators
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Chu, Crystal K.
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Liang, Yufan
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Fu, Gregory C.
Abstract
A wide array of cross-coupling methods for the formation of C–C bonds from unactivated alkyl electrophiles have been described in recent years. In contrast, progress in the development of methods for the construction of C–heteroatom bonds has lagged; for example, there have been no reports of metal-catalyzed cross-couplings of unactivated secondary or tertiary alkyl halides with silicon nucleophiles to form C–Si bonds. In this study, we address this challenge, establishing that a simple, commercially available nickel catalyst (NiBr_2·diglyme) can achieve couplings of alkyl bromides with nucleophilic silicon reagents under unusually mild conditions (e.g., −20 °C); especially noteworthy is our ability to employ unactivated tertiary alkyl halides as electrophilic coupling partners, which is still relatively uncommon in the field of cross-coupling chemistry. Stereochemical, relative reactivity, and radical-trap studies are consistent with a homolytic pathway for C–X bond cleavage.
Additional Information
© 2016 American Chemical Society. Received: April 4, 2016. Publication Date (Web): May 17, 2016. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R01-GM62871) and the Gordon and Betty Moore Foundation (Caltech Center for Catalysis and Chemical Synthesis). We thank Dr. Alexander S. Dudnik for preliminary observations and Dr. Junwon Choi for helpful discussions. The authors declare no competing financial interest.Attached Files
Accepted Version - nihms815606.pdf
Supplemental Material - ja6b03465_si_001.pdf
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Additional details
- PMCID
- PMC5031417
- Eprint ID
- 67285
- Resolver ID
- CaltechAUTHORS:20160524-081446502
- NIH
- R01-GM62871
- Gordon and Betty Moore Foundation
- Created
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2016-05-24Created from EPrint's datestamp field
- Updated
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2022-04-27Created from EPrint's last_modified field