Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 28, Pages 15254-15259Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202103429
Keywords
carbene equivalents; 1; 2-dicarbonyl compounds; homogeneous catalysis; molybdenum; regiospecific deoxygenation
Categories
Funding
- Recruitment Program of Global Experts and Xiamen University
Ask authors/readers for more resources
The study describes a Mo-catalyzed regiospecific deoxygenative cyclopropanation reaction using readily available 1,2-dicarbonyl compounds, which efficiently produces substituted cyclopropanes with high selectivity and synthetic utility. Preliminary mechanistic studies suggest that phosphine (or silane) acts as both a mild reductant and a good oxygen acceptor, efficiently regenerating the catalytically active Mo catalyst.
The transition-metal-catalyzed cyclopropanation of alkenes by the decomposition of diazo compounds is a powerful and straightforward strategy to produce cyclopropanes, but is tempered by the potentially explosive nature of diazo substrates. Herein we report the Mo-catalyzed regiospecific deoxygenative cyclopropanation of readily available and bench-stable 1,2-dicarbonyl compounds, in which one of the two carbonyl groups acts as a carbene equivalent upon deoxygenation and engages in the subsequent cyclopropanation process. The use of a commercially available Mo catalyst afforded an array of valuable cyclopropanes with exclusive regioselectivity in up to 90 % yield. The synthetic utility of this method was further demonstrated by gram-scale syntheses, late-stage functionalization, and the cyclopropanation of a simple monocarbonyl compound. Preliminary mechanistic studies suggest that phosphine (or silane) acts as both a mild reductant and a good oxygen acceptor that efficiently regenerates the catalytically active Mo catalyst through reduction of the Mo-oxo complexes.
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