Journal
CHEMISTRY-AN ASIAN JOURNAL
Volume 13, Issue 18, Pages 2606-2610Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/asia.201800934
Keywords
1,3-diketones; C-C bond insertion; diazo compounds; synthetic methods; quaternary carbons
Categories
Funding
- National Natural Science Foundation of China [21625204]
- 111 project of the Ministry of Education of China [B06005]
- National Program for Special Support of Eminent Professionals
- Fundamental Research Funds for the Central Universities
Ask authors/readers for more resources
The transition-metal-catalyzed formal C-C bond insertion reaction of diazo compounds with monocarbonyl compounds is well established, but the related reaction of 1,3-diketones instead gives C-H bond insertion products. Herein, we report a protocol for a gold-catalyzed formal C-C bond insertion reaction of 2-aryl-2-diazoesters with 1,3-diketones, which provides efficient access to polycarbonyl compounds with an all-carbon quaternary center. The aryl ester moiety plays a crucial role in the unusual chemoselectivity, and the addition of a Bronsted acid to the reaction mixture improves the yield of the C-C bond insertion product. A reaction mechanism involving cyclopropanation of a gold carbenoid with an enolate and ring-opening of the resulting donor-acceptor-type cyclopropane intermediate is proposed. This mechanism differs from that of the traditional Lewis-acid-catalyzed C-C bond insertion reaction of diazo compounds with monocarbonyl compounds, which involves a rearrangement of a zwitterion intermediate as a key step.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available