| Title: | "The reactivity of epoxides with lithium 2,2,6,6-tetramethylpiperidide in combination with organolithiums or grignard reagents" |
| Author(s): | Hodgson DM; Fleming MJ; Stanway SJ; |
| Address: | "Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA, United Kingdom. david.hodgson@chem.ox.ac.uk" |
| ISSN/ISBN: | 0022-3263 (Print) 0022-3263 (Linking) |
| Abstract: | "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" |
| Keywords: | Acetates/chemistry Alkenes/chemistry Amides/chemistry Deuterium/chemistry Dodecanol/analogs & derivatives Epoxy Compounds/*chemistry Lithium Compounds/*chemistry Molecular Structure Organometallic Compounds Pyridines/*chemistry Sex Attractants Silanes/che; |
| Notes: | "MedlineHodgson, David M Fleming, Matthew J Stanway, Steven J eng Research Support, Non-U.S. Gov't 2007/05/29 J Org Chem. 2007 Jun 22; 72(13):4763-73. doi: 10.1021/jo070291v. Epub 2007 May 26" |
