Highly stereoselective synthesis of cyclopentanes bearing four stereocentres by a rhodium carbene-initiated domino sequence

Brendan T Parr and Huw M.L. Davies ()
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Brendan T Parr: Emory University
Huw M.L. Davies: Emory University

Nature Communications, 2014, vol. 5, issue 1, 1-12

Abstract: Abstract Stereoselective synthesis of a cyclopentane nucleus by convergent annulation constitutes a significant challenge for synthetic chemists. Although a number of biologically relevant cyclopentane natural products are known, more often than not, the cyclopentane core is assembled in a stepwise manner because of the lack of efficient annulation strategies. Here we report the rhodium-catalysed reactions of vinyldiazoacetates with (E)-1,3-disubstituted 2-butenols generate cyclopentanes, containing four new stereogenic centres with very high levels of stereoselectivity (99% ee, >97: 3 dr). The reaction proceeds by a carbene-initiated domino sequence consisting of five distinct steps: rhodium-bound oxonium ylide formation, [2,3]-sigmatropic rearrangement, oxy-Cope rearrangement, enol—keto tautomerization and finally an intramolecular carbonyl ene reaction. A systematic study is presented detailing how to control chirality transfer in each of the four stereo-defining steps of the cascade, consummating in the development of a highly stereoselective process.

Date: 2014
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DOI: 10.1038/ncomms5455

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