104602-93-9Relevant academic research and scientific papers
β-(Carbonatoxy)alkyl radicals: A new subset of β-(ester)alkyl radical fragmentation during copper(I)-mediated synthesis of 1,1-dichloro-1-alkenes
Ram, Ram N.,Tittal, Ram K.
supporting information, p. 4342 - 4345 (2014/07/22)
A new subset of β-(ester)alkyl radicals is presented. It is the first study on the chemistry of β-(alkoxycarbonyloxy)alkyl radicals that fill the gap in the spectrum of the migrating groups in β-(ester)alkyl radical reactions. The change from less nucleofugal (acetate) group to the more nucleofugal (carbonate) group in the spectrum of the migrating group changed the reaction path from rearrangement to fragmentation. This approach has been used for the synthesis of 1,1-dichloroalkenes in high yields. The formation of dichloroalkenes was accounted by the involvement of alkene radical cation and carbonate anion pair (a CIP) as a result of heterolysis of the CO bond of the carbonate at the β-position of the β-(alkoxycarbonyloxy)alkyl radical. The alkene radical cation was trapped by nucleophilic reaction with MeOH to form methyl ester.
General and practical conversion of aldehydes to homologated carboxylic acids
Cafiero, Lauren R.,Snowden, Timothy S.
supporting information; experimental part, p. 3853 - 3856 (2009/07/01)
(Chemical Equation Presented) The reaction of aldehydes with trichloromethide followed by sodium borohydride or sodium phenylseleno(triethyl) borate under basic conditions affords homologated carboxylic acids in high yields. This operationally simple procedure provides a practical, efficient alternative to other homologation protocols. The approach is compatible with sensitive aldehydes including enals and enolizable aldehydes. It also offers convenient access to α-monodeuterated carboxylic acids.
Copper(I)-promoted synthesis of chloromethyl ketones from trichloromethyl carbinols
Ram, Ram N.,Manoj
, p. 5633 - 5635 (2008/12/21)
(Chemical Equation Presented) Reaction of several trichloromethyl carbinols with 2 equiv of CuCl/bpy in refluxing DCE for 3 h afforded chloromethyl ketones in excellent yield by 1,2-H shift in the copper-chlorocarbenoid intermediate.
Fluoride Ion-Catalyzed Generation and Carbonyl Addition of α-Halo Carbanions Derived from α-Halo Organosilicon Compounds
Fujita, Makoto,Obayashi, Michio,Hiyama, Tamejiro
, p. 4135 - 4146 (2007/10/02)
The title carbanion species are generated from the corresponding α-haloorganosilicon compounds by the action of a catalytic amount of tris(diethylamino)sulfonium difluorotrimethylsilicate and are found to undergo addition to aldehyde carbonyl efficiently at ambient temperature.The synthetic potential of the reaction is demonstrated by application to the synthesis of some insecticides.
