James E. Audia

Diels-alder cyclization of 2,8,10-undecatrienals as a route to 1,2,3,4,4a,5,6,8a-octahydronaphthalenes

Abstract 2,8,10-Undecatrienals have been found to undergo facile Diels-Alder cyclization upon treatment with alkylaluminum chlorides in methylene chloride at low temperature. The reaction is highly endo-selective. Protected alcohol substituents at the C-4 and C-7 positions are fully accommodated and TBDMS protected alcohols show a strong axial preference. The methodology has been applied to a hydronaphthalenecarboxylic add of possible use in a projected total synthesis of the macrocyclic antitumor antibiotic, chlorothricolide.

Improved Preparation of (E)-3-Trimethylsilyl-2-Buten-1-OL

Abstract An improved preparation of (E)-3-trimethylsilyl-2-buten-1-ol is described. The two-step process entails stereo-selective addition of (TMS)2 CuLi-LiCN to ethyl tetrolate followed by reduction with diisobutylaluminum hydride and proceeds in 90% overall yield.