- Reductive tert-butylation of anils by tert-butylmercury halides
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tert-Butyl radicals add to the carbon atom of benzylideneanilines to form anilino radicals, which are protonated in the presence of PTSA or NH4+ in Me2SO. Reduction of the resulting aniline radical cations occurs readily by the ate complex, t-BuHgI2. In the absence of a proton donor, f-BuHgI will also transfer a hydrogen atom to the anilino radical to give the reductive alkylation product. Protonation can promote a free radical chain process involving electron transfer by substrate activation and/or by increasing the electron affinity of the intermediate radicals. Since the adduct radicals formed from benzylideneanilines are more easily protonated than the parent Schiff bases, PTSA but not NH4+ demonstrates substrate activation, although both proton donors promote the free radical reaction.
- Russell, Glen A.,Wang, Lijuan,Rajaratnam, Ragine
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p. 8988 - 8991
(2007/10/03)
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- Reactions of (Benzothiazol-2-ylthio)(trimethylsilyl)methane. A General Method for α-Mercaptoalkylation by Alkylation and Alkylative Desilylation
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Readily available (benzothiazol-2-ylthio)(trimethylsilyl)methane (2a) provides a convenient synthon for HSCH2- and enables the general conversions RR'CO -> RR'C(OH)CH(SH)R'' and RBr -> RCH(SH)SiMe3.The lithium derivative of 2a reacts with aldehydes and ketones to give Peterson olefination products which are protected vinyl mercaptans converted into vinyl mercaptans by reaction with methyllithium.This overall conversion is RR'CO -> RR'C:CHSH.
- Katritzky, Alan R.,Kuzmierkiewicz, Wojciech,Aurrecoechea, Jose M.
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p. 844 - 849
(2007/10/02)
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- REACTION OF BENZOTHIAZOLINE WITH BENZYNE - GENERATION OF NOVEL HETEROCYCLIC SULFUR YLIDE, BENZOTHIAZOLINIUM S-YLIDE
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A novel heterocyclic sulfur ylide, 2-t-butyl-3-methyl-1-phenylbenzothiazolinium ylide (13) was generated as an intermediate in the reaction of 2-t-butyl-3-methylbenzothiazoline (2) with benzyne.The S-ylide 13 underwent a novel intermolecular shift to give 2-t-butyl-3-methyl-2-phenylbenzothiazoline .
- Hori, Mikio,Kataoka, Tadashi,Shimizu, Hiroshi,Ueda, Norihiro
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p. 3071 - 3074
(2007/10/02)
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