Enantioselective Synthesis of Paraconic Acids

Abstract
The development of a new method for the enantioselective synthesis of disubstituted γ-butyrolactones is reported. Based on this strategy, the total synthesis of three paraconic acids, that is (−)-roccellaric acid, (−)-nephrosteranic acid and (−)-protopraesorediosic acid, and the formal total synthesis of (−)-methylenolactocin and (−)-protolichesterinic acid is described, which are important because of their antibiotic and antitumor properties. Key steps of the synthesis are copper(I)-catalyzed asymmetric cyclopropanations of furans, highly diastereoselective Sakurai allylations, Lewis acid or Lewis base catalyzed retroaldol/lactonization cascades, and ruthenium(II)-catalyzed, intermolecular cross metathesis reactions.

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