34349-70-7Relevant articles and documents
Catalytic Intermolecular C(sp3)-H Amination: Selective Functionalization of Tertiary C-H Bonds vs Activated Benzylic C-H Bonds
Brunard, Erwan,Boquet, Vincent,Van Elslande, Elsa,Saget, Tanguy,Dauban, Philippe
, p. 6407 - 6412 (2021/05/29)
A catalytic intermolecular amination of nonactivated tertiary C(sp3)-H bonds (BDE of 96 kcal·mol-1) is reported for substrates displaying an activated benzylic site (BDE of 85 kcal·mol-1). The tertiary C(sp3)-H bond is selectively functionalized to afford α,α,α-Trisubstituted amides in high yields. This unusual site-selectivity results from the synergistic combination of Rh2(S-Tfpttl)4, a rhodium(II) complex with a well-defined catalytic pocket, with tert-butylphenol sulfamate (TBPhsNH2), which leads to a discriminating rhodium-bound nitrene species under mild oxidative conditions. This catalytic system is very robust, and the reaction was performed on a 50 mmol scale with only 0.01 mol % of catalyst. The TBPhs group can be removed under mild conditions to afford the corresponding NH-free amines.
Facile Hydrogenolysis of C(sp3)–C(sp3) σ Bonds
Fillion, Eric,Beaton, Eric,Nguyen, Yen,Wilsily, Ashraf,Bondarenko, Ganna,Jacq, Jér?me
supporting information, p. 3422 - 3434 (2016/11/13)
The modification of benzylic quaternary, tertiary, and secondary carbon centers through palladium-catalyzed hydrogenolysis of C(sp3)–C(sp3) σ bonds is presented. When benzyl Meldrum's acid derivatives bearing quaternary benzylic centers are treated under mild hydrogenolysis conditions – palladium on carbon and atmospheric pressure of hydrogen – aromatics substituted with tertiary benzylic centers and Meldrum's acid are obtained with good to excellent yield. Analogously, substrates containing tertiary or secondary benzylic centers yield aromatics substituted with secondary benzylic centers or toluene derivatives, respectively. Furthermore, this strategy is used for the high yielding synthesis of diarylmethanes. The scope of the reductive dealkylation reaction is explored and the limitations with respect to steric and electronic factors are determined. A mechanistic analysis of the reaction is described that consisted of deuterium labelling experiments and hydrogenolysis of enantioenriched derivatives. The investigation shows that the C(sp3)–C(sp3) σ bond-cleaving events occur through a hybrid SN1/SN2 mechanism, in which the palladium center displaces a carbon-based leaving group, namely Meldrum's acid, with inversion of configuration, followed by reductive elimination of palladium to furnish a C?H bond. (Figure presented.).
Non-catalytic conversion of C-F bonds of benzotrifluorides to C-C bonds using organoaluminium reagents
Terao, Jun,Nakamura, Misaki,Kambe, Nobuaki
supporting information; experimental part, p. 6011 - 6013 (2010/11/16)
A facile method for the conversion of C-F bonds of benzotrifluorides to C-C bonds has been developed using aluminium reagents in the absence of catalysts.
