Molybdenum‐Catalyzed Deoxygenative Cyclopropanation of 1,2‐Dicarbonyl or Monocarbonyl Compounds

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 deoxygenati...

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Bibliographic Details
Published in:Angewandte Chemie 2021-07, Vol.133 (28), p.15382-15387
Main Authors: Cao, Li‐Ya, Luo, Jian‐Nan, Yao, Jia‐Sheng, Wang, De‐Ku, Dong, Yuan‐Qing, Zheng, Chao, Zhuo, Chun‐Xiang
Format: Article
Language:English
Subjects:
1,2-dicarbonyl compounds
Alkenes
carbene equivalents
Carbonyl compounds
Carbonyl groups
Carbonyls
Catalysts
Chemistry
Deoxygenation
homogeneous catalysis
Molybdenum
Organic compounds
Phosphine
Phosphines
Reducing agents
Regioselectivity
regiospecific deoxygenation
Substrates
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Summary: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. Readily available and bench‐stable 1,2‐dicarbonyl compounds are shown to undergo Mo‐catalyzed regiospecific deoxygenative cyclopropanation. This method has led to an array of valuable cyclopropanes in yields of up to 90 % and with exclusive regioselectivity. This strategy was further applied to the cyclopropanation of a simple monocarbonyl compound.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202103429