Enantioselective Synthesis of Bicyclo[4.4.1]undecane-2,7-dione via ­Samarium(II)-Mediated Fragmentation of a Cyclopropane Precursor

Abstract

An efficient six-step synthesis of bicyclo[4.4.1]undecane-2,7-dione was elaborated. Key steps include an enantioselective oxazaborolidine-catalyzed borane reduction (CBS reduction) of 2,3,4,6,7,8-hexahydronaphthalene-1,5-dione to the corresponding diol, and a subsequent (syn-diastereoselective) cyclopropanation. Oxidation then gives tricyclo[4.4.1.0^1,6]undecane-2,7-dione (>99% ee) which on treatment with two equivalents of samarium(II) iodide undergoes cleavage of the central cyclopropane bond to yield the target compound without any loss of stereochemical information.

Key words

asymmetric synthesis - chirality - cyclopropane - fragmentation - samarium diiodide

References and Notes

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