1,(w-1)-Dienes: solvent controlled unilateral or bilateral metalation

In hexane, i.e. under heterogeneous conditions, 1,(w - 1)-dienes readily undergo double deprotonation to give bis(allylmetal) intermediates. In THF at -75 or -50 Deg, however, only monometalation occurs with dienes having <C12 chains. Thus, treatment of 1,7-octadiene with BuLi-KOCMe3 in hexane, followed by MeI, gave (Z)-3-methyl-1,6-nonadiene and (3Z,7Z)-3,7-decadiene; whereas, in THF, with hexane stripped from the BuLi, 3-methyl-1,7-octadiene and (Z)-1,6-nonadiene were obtained. The practical potential of the selective monosubstitution reaction is demonstrated by two novel pheromone syntheses. [on SciFinder (R)]

Published in:
Journal of Organometallic Chemistry, 409, 1-2, 83-91
CAN 115:91875 26-2 Biomolecules and Their Synthetic Analogs Inst. Chim. Org.,Univ. Lausanne,Lausanne,Switz. Journal 0022-328X written in English. 592-42-7 (1,5-Hexadiene); 1647-16-1 (1,9-Decadiene); 3710-30-3 (1,7-Octadiene); 4900-30-5 (1,8-Nonadiene); 21964-49-8 (1,13-Tetradecadiene) Role: RCT (Reactant), RACT (Reactant or reagent) (metalation and methylation of); 13688-67-0 (1,10-Undecadiene) Role: RCT (Reactant), RACT (Reactant or reagent) (metalation and reaction of, with iodopropoxytetrahydropyran); 66410-24-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and acetylation of); 13151-11-6P; 13151-22-9P; 20996-35-4P; 28465-80-7P; 53120-27-7P; 91914-00-0P; 92230-33-6P; 106694-77-3P; 135346-19-9P; 135346-20-2P; 135346-21-3P; 135346-22-4P; 135346-23-5P; 135346-24-6P; 135346-25-7P; 135346-26-8P; 135346-27-9P; 135346-28-0P; 135346-29-1P; 135346-30-4P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of); 81500-71-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn., metalation, and alkylation of); 110-62-3 (Pentanal) Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with dodecenyltriphenylphosphonium iodide); 135346-18-8 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with pentanal); 52103-12-5 Role: RCT (Reactant), RACT (Reactant or reagent) (reaction of, with undecadiene)

 Record created 2006-03-03, last modified 2018-01-27

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