Ranked among the 10 most used cycles for the elaboration of small drug molecules,[1] the cyclopropane subunit is a key backbone for the pharmaceutical industry. Thus, new strategies to access and allow efficient functionalization of such moieties are needed. Recently, our group published various cyclopropanation reactions to access chloro-,[2] fluoro-[3] and iodocyclopropanes[4] in good yields and presenting excellent selectivities, starting from allylic alcohols. However, no method has ever been described so far to access enantioenriched bromocyclopropanes from alkenes,.[5],[6],[7],[8] In this presentation, we will present the first enantioselective bromocyclopropanation reaction of allylic alcohols. An in-depth NMR study of the reagents will also be presented. These spectroscopic studies allowed us not only to optimize the conditions used for the formation of the reagent but also to minimize the formation of undesired by-products. [1] Taylor, R. D.; MacCoss, M.; Lawson, A. D. G. J. Med. Chem. 2014, 57, 5845. [2] Beaulieu, L.-P. B.; Zimmer, L. E.; Gagnon, A.; Charette, A. B. Chem. Eur. J. 2012, 18, 14784. [3] Beaulieu, L.-P. B.; Schneider, J. F.; Charette, A. B. J. Am. Chem. Soc. 2013, 135, 7819. [4] Beaulieu, L.-P. B.; Zimmer, L. E.; Charette, A. B. Chem. Eur. J. 2009, 15, 11829. [5] Overman, L. E.; Ricca, D. J.; Tran, V. D. J. Am. Chem. Soc. 1997, 119, 12031. [6] Shi, J.; Manolikakes, G.; Yeh, C.-H.; Guerrero, C. A.; Shenvi, R. A.; Shigehisa, H.; Baran, P. S. J. Am. Chem. Soc. 2011, 133, 8014. [7] Tucker, J. W.; Stephenson, C. R. J. Org. Lett. 2011, 13, 5468. [8] Banning, J. E.; Gentillon, J.; Ryabchuk, P. G.; Prosser, A. R.; Rogers, A.; Edwards, A.; Holtzen, A.; Babkov, I. A.; Rubina, M.; Rubin, M. J. Org. Chem. 2013, 78, 7601.

Development of an enantio- and diastereoselective Simmons-Smith bromocyclopropanation reaction and mechanistic considerations

249th National Meeting (2015)

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