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Synlett 2011(17): 2437-2442  
DOI: 10.1055/s-0031-1289520
SYNPACTS
© Georg Thieme Verlag Stuttgart ˙ New York

Buchner and Beyond: Arene Cyclopropanation as Applied to Natural Product Total Synthesis

Sarah E. Reisman*, Roger R. Nani, Sergiy Levin
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineer­ing, California Institute of Technology, Pasadena, California 91125, USA
Fax: +1(626)3958436; e-Mail: reisman@caltech.edu;
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Publikationsverlauf

Received 25 April 2011
Publikationsdatum:
06. Oktober 2011 (online)

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Abstract

Buchner and Curtius first reported the cyclopropanation of arenes in 1885. Since the initial discovery, the Buchner reaction has been the subject of significant research by both physical and synthetic organic chemists. Described herein is a brief overview of the Buchner reaction and related arene cyclopropanation processes, with an emphasis on their application to natural product total synthesis.

Key words

Buchner - cyclopropanation - diazo - norcaradiene - cycloheptatriene - total synthesis

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27

Cyclopentanones i and ii were determined to be the major byproducts (Figure  [²] ).

28

Substrates 35b and 35c were screened against an array of rhodium and copper catalysts; Table  [¹] , entries 9 and 10 represent the best catalysts identified for the formation of 36b and 36c, respectively.

31

Ketoaldehyde iii (Figure  [³] ) is also formed in 36% yield; iii can be converted into 32 using catalytic Rh(cod)Cl2 and diphenylphosphinopropane. See: Phan D. H. T., Kim B., Dong V. M.; J. Am. Chem. Soc.; 2009, 131: 156