223. Asymmetric synthesis of highly functionalized cyclopentanes by a rhodium- and scandium-catalyzed five-step domino sequence

Authors: Brendan T. Parr, Zhanjie Li and Huw M. L. Davies

Chem. Sci.,

2011, 2, 2378-2382

041

A domino sequence has been developed between vinyldiazoacetates and racemic allyl alcohols, involving five distinct steps. The sequence generates highly functionalized cyclopentanes with four new stereogenic centers as single diastereomers in 64–92% ee. The first step is a rhodium-catalyzed oxygen ylide formation, which is then followed by a [2,3]-sigmatropic rearrangement, an oxy-Cope rearrangement, a keto/enol tautomerization, and then finally a carbonyl ene reaction. With appropriate substrates, a further silyl deprotection and a 6-exo-trig cyclization can be added to the domino process.

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