Transition-Metal-Mediated Cascade Reactions: The Water-Accelerated Carboalumination−Claisen Rearrangement−Carbonyl Addition Reaction
The Journal of Organic Chemistry2005Vol. 70(20), pp. 8096–8102
Citations Over TimeTop 18% of 2005 papers
Abstract
A three-step cascade reaction involving a water-accelerated catalytic carboalumination, a Claisen rearrangement, and a nucleophilic carbonyl addition converts terminal alkynes and allyl vinyl ethers into allylic alcohols containing up to three contiguous asymmetric carbon centers. Stoichiometric quantities of water as an additive increase the rate of the [3,3] sigmatropic rearrangement as well as the diastereoselectivity of the carbonyl addition process. Reaction products contain 1,6-diene functionalities that are readily cyclized to substituted cyclopentenes. An extension of this methodology to a sequence involving a [1,3] sigmatropic shift was feasible with a cyclopropylmethyl vinyl ether substrate.
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