Enantioselective Synthesis of Complex Carbocycles by C–H Insertion of Aryl/Aryl Carbenes
A range of benzene and indole-fused carbocyclic molecules were accessed by the enantioselective C–H insertion of rhodium aryl/aryl carbenes. 1,4, 1,5, and 1,6 C–H insertion reactions are chemoselective for insertion into carbon centers appended with an electron-donating heteroatom. Examples include a range of ethers, a free hydroxyl group, and a range of nitrogen substituents, including basic amines. DFT calculations support a stepwise mechanism of this process and provide insight into the origin of both stereoselectivity and the preference for C–H versus O–H insertion.
Authors
- Matthew S. Sigman (ORCID: https://orcid.org/0000-0002-5746-8830)
- Beck Miller (ORCID: https://orcid.org/0009-0006-2487-6690)
- Damon Turner
- Wentao Guo (ORCID: https://orcid.org/0000-0001-8058-8323)
- Jared T. Shaw (ORCID: https://orcid.org/0000-0001-5190-493X)
- Emily Jimenez (ORCID: https://orcid.org/0000-0003-1694-4818)
- Jose M. Ruiz (ORCID: https://orcid.org/0000-0002-1164-1060)
- Wang‐Yeuk Kong (ORCID: https://orcid.org/0000-0002-4592-0666)
- James C. Fettinger (ORCID: https://orcid.org/0000-0002-6428-4909)
- Mingchun Gao (ORCID: https://orcid.org/0000-0002-8564-4387)
- Dean J. Tantillo (ORCID: https://orcid.org/0000-0002-2992-8844)
- Tania Shahvali
Institutions
- University of Utah (US)
- University of California System (US)
Publication Details
- Journal
- ACS Catalysis
- Published
- 2025-09-10
- DOI
- https://doi.org/10.1021/acscatal.5c04528
- Citations
- 2
- Primary Topic
- Cyclopropane Reaction Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 1.87