69820-25-3Relevant articles and documents
The reactivity of epoxides with lithium 2,2,6,6-tetramethylpiperidide in combination with organolithiums or grignard reagents
Hodgson, David M.,Fleming, Matthew J.,Stanway, Steven J.
, p. 4763 - 4773 (2008/02/04)
(Chemical Equation Presented) The scope and limitations of lithium 2,2,6,6-tetramethylpiperidide (LTMP)-modified reductive alkylation of epoxides is detailed. A variety of organolithiums are added to terminal and 2,2-disubstituted epoxides in the presence of LTMP to generate alkenes in a completely regio- and highly stereoselective manner. Arylated alkenes, dienes, allylsilanes, and enynes are accessed using this procedure. The methodology is applied in the synthesis of the roller leaf moth pheromone, (3E,5Z)-dodecadienyl acetate. The corresponding reaction without LTMP has also been examined, and a study using deuterated epoxides provides insight into the mechanism. In the presence of LTMP, Grignard reagents are also shown to produce E-alkenes directly from epoxides.
