Trichloromethyl group reduction

Rather a nucleophilic reduction of the trichloromethyl group appears most likely since the three chlorines in close proximity may attract electrons from a reduced enzymatic prosthetic group (e.g., a reduced metal, Mered) ... 

Bulk electrolysis of the crossconjugated dienone 122 (Eq. (192) ) gave 96% of the pinacol 123 in acidic or basic medium. With the analogous methyltrichloro-methyl derivative 124, the pinacol yield dropped to 10%, but 76% of p-cresol was formed, probably by reductive elimination of the trichloromethyl group 417). 

The trichloromethyl group can be reduced to either the dichloro- or the monochloromethyl group by proper choice of the SSE 49 s With ammonium nitrate the dichloro compounds are formed in 64—94% yield, while with tetra-metliylammonium chloride as supporting electrolyte the monochloro derivatives are obtained in 63 to 95% yield. As trichloromethyl compounds are readily available by telomerization of olefins with CC14) this reduction opens a simple route to a, co-bifunctional aliphatic compounds. 

The expected reactions of the cyano group attached to triazine ring carbon with amine, alcohol, and azide nucleophiles have been described <90NKK396>. Reduction of ketone to alcohol with sodium borohydride <88HCA712> and trichloromethyl groups to methyls with lithium aluminum hydride are also reported <86MI 6l2-02>. 

Hydrolyses of perchloroalkylbenzenes and related chlorocarbons Nucleophilic attack on perchloroalkylbenzenes and related compounds dealkylations 294 Reductive condensations of perchlorotoluene and other highly chlorinated trichloromethyl chlorocarbons 298 Alkylation of trichloromethyl compounds with trialkyl phosphites A conversion of trichloromethyl groups into cyano groups 312... 

Shimizu et al. have reported the synthesis of the 4-hydroxy-6-lactone component of mevinic acid by lactonization of a 6-hydroxy ester [53] (Scheme 16). Reaction of lithio-fcrt-butylacetate with p-trichloromethyl-p-lactone 80 gave 6-hydroxy-p-keto ester 81. A stereoselective syn reduction of the ketone, lactcmization, and protection of the secOTidaiy alcohol provided the lactone. The trichloromethyl group was reduced with tri- -butyltin hydride to furnish 6-chloromethyl lactone intermediate 84. 

From a-trichloromethyl carbinols with the hydroxy group at a tertiary carbon, either dichlorovinyl compounds or, after rearrangement, carbonyl compounds are formed predominantly. The pathway of the reaction can be influenced by the choice of the reaction conditions. As the reduction potentials of some of the substrates are... 

Carbon tetrachloride undergoes stepwise reduction at mercury in DMF containing TEABr [45]. Several groups of workers [46-52] have electrogenerated the shortlived trichloromethyl anion, which can react with acrylonitrile, ethyl acrylate, diethyl fumarate, alkyl monohalides, and a variety of aldehydes and ketones. De Angelis and coworkers [53] have used dichlorocarbene, generated via reduction of carbon tetra-... 

This reaction was first reported by Corey and T.ink in 1992. It is an enantioselective synthesis of a -amino acids by means of the asymmetric reduction of trichloromethyl ketones from catechoiborane in the presence of either (/ )- or (5)-oxazaborolidine, followed by the treatment of the resulting alcohols with base and sodium azide and subsequently the reductive conversion of the azido group into an amino group. Therefore, this reaction is generally known as the Corey-Link reaction. Occasionally, it is also referred to as the Corey-Link amino acid synthesis, Corey-Link procedure, etc. 

The VNS of hydrogen in l-benzyl-4-nitroimidazole by action of trichloromethyl carbanion results in the formation of 5-dichloromethyl derivative (Scheme 29). Hydrolysis and condensation of the resulting aldehyde with diethyl malonate afford the corresponding alkene that, upon reduction of the nitro group, undergoes cycli-... 

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