☆ 4.8 Article

Stereoselective Rh2(S-IBAZ)4-Catalyzed Cyclopropanation of Alkenes, Alkynes, and Allenes: Asymmetric Synthesis of Diacceptor Cyclopropylphosphonates and Alkylidenecyclopropanes

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2013)

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

卷 135, 期 4, 页码 1463-1470

出版社

AMER CHEMICAL SOC

DOI: 10.1021/ja3099728

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Chemistry, Multidisciplinary

资金

Natural Science and Engineering Research Council of Canada (NSERC)
Canada Research Chair Program
Canada Foundation for Innovation
Centre in Green Chemistry and Catalysis (CGCC)
Universite de Montreal

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A mild and highly stereoselective rhodium(II)-catalyzed cyclopropanation of alkenes, alkynes, and allenes with diacceptor diazo compounds is reported. Using the phosphonate moiety as an efficient trans-directing group, the first catalytic asymmetric route to diacceptor cycloprop(en)ylphosphonates was developed by employing an alpha-cyano diazophosphonate and Rh-2(S-IBAZ)(4) as chiral catalyst. The isosteric character of phosphonic and carboxylic acid derivatives allowed the alternative use of an alpha-cyano diazo ester in the process, leading to alpha-cyano cycloprop(en)ylcarboxylates in high yields and stereoselectivities. Taking advantage of the particular reactivity of the cyanocarbene intermediates involved in this system, the scope of compatible substrates could be extended to substituted allenes, leading to the development of the first catalytic enantioselective method for the synthesis of diacceptor alkylidenecyclopropanes.

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