Facile Hydrogenolysis of C(sp3)-C(sp3) σ Bonds

被引:13
|
作者
Fillion, Eric [1 ]
Beaton, Eric [1 ]
Nguyen, Yen [1 ]
Wilsily, Ashraf [1 ]
Bondarenko, Ganna [1 ]
Jacq, Jerome [1 ]
机构
[1] Univ Waterloo, Dept Chem, Waterloo, ON N2L 3G1, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
diarylmethane; hydrogenolysis; Meldrum's acid; quaternary centers; reductive dealkylation; CROSS-COUPLING REACTIONS; CARBON-CARBON BONDS; CATALYTIC HYDROGENOLYSIS; INTRAMOLECULAR ARYLCYANATION; BENZYLIC ALCOHOLS; MELDRUMS ACID; LEAVING GROUP; CLEAVAGE; HYDROGENATION; METAL;
D O I
10.1002/adsc.201600535
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
The modification of benzylic quaternary, tertiary, and secondary carbon centers through palladium-catalyzed hydrogenolysis of C(sp(3))-C(sp(3)) sigma 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(sp(3))-C(sp(3)) sigma bond-cleaving events occur through a hybrid S(N)1/S(N)2 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.
引用
收藏
页码:3422 / 3434
页数:13
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