39761-61-0Relevant academic research and scientific papers
Competing Radical, Carbanion, and Carbene Pathways in the Reactions of Hindered Primary Alkyl Halides with Lithium Dialkylamides
Ashby, E. C.,Park, B.,Patil, G. S.,Gadru, K.,Gurumurthy, R.
, p. 424 - 437 (2007/10/02)
A variety of methods were utilized to study the mechanism of reaction of 6-iodo-5,5-dimethyl-1-hexene and its bromo, chloro, and tosylate derivatives with LDA and several other lithium dialkylamides.In the reaction of 6-iodo-5,5-dimethyl-1-hexene with LDA in THF, radical, carbanion, and carbene pathways occured simultaneously.However, when the corresponding bromide was allowed to react with LDA, the radical pathway was minor and when the corresponding chloride or tosylate was allowed to react with LDA, no evidence for radical products was observed.This is the first time that competing radical, carbanion, and carbene pathways have been detected in the reaction of a primary alkyl halide with any nucleophile.
AN EASY SYNTHESIS OF THE 2-PHENYLSULFONYL-SUBSTITUTED ALLYLIC BROMIDES AND ACETATES AND THEIR REACTIVITY TOWARDS NUCLEOPHILES
Auvray, P.,Knochel, P.,Normant, J. F.
, p. 5095 - 5098 (2007/10/02)
The reaction of phenyl vinyl sulfone with various aldehydes in the presence of a catalytic amount of DABCO furnishes in good yields the corresponding 2-phenylsulfonyl-substituted alcohols 5a-5e which can be easily converted into their acetates 2a-2b or into their allylically rearranged bromides 3a-3d.These reagents, in turn, react with nucleophiles (ketone enolates and cuprates) with an allylic rearrangement (SN2' mechanism) to give the functionalized unsaturated sulfones 6a-g and 7a-g.A palladium catalyzed reaction allows a stereo-controlled transformation of the sulfone 6b into the (Z,Z) skipped 1,4-diene 8.
