Table of ContentsWith the aid of a base, a highly efficient visible-light-driven aerobic dehydrogenation of 2-subsituted dihydropyrimidines and phenolic imines has been achieved. COMMUNICATION This journal isAn efficient visible-light-driven photocatalytic oxidation of various 2-subsituted dihydropyrimidines and phenolic imines has been achieved by using organic photocatalyst eosin Y bis(tetrabutyl ammonium salt) (TBA-eosinY) and inexpensive oxidant molecular oxygen. With the aid of a base, significantly enhanced photoinduced electron transfer from substrates dihydropyrimidines or phenolic imines to the excited state of TBA-eosinY has enabled the aerobic oxidation to yield 2-(methylthio)pyrimidines or 2-arylbenzoxazoles selectively.

A versatile dual H-bonds and π–π interaction strategy that enables enantioselective remote C6-selective C–H functionalization of 2,3-disubstituted indoles was first reported. The N–H bond of indole was pivotal to achieve the C6 functionalization with excellent yield and enantioselectivity. Furthermore, this methodology leads to the efficient construction of numerous enantioenriched C6-functionalized indole products under mild reaction conditions employing different electrophiles. Preliminary cell proliferation investigations revealed that the synthesized chiral C6-substituted indole derivatives had potential anticancer activities.

An efficient and convenient palladium-catalyzed direct intermolecular silylation of C(sp)-H bonds by using disilanes as the silicon source with the assistance of a readily removable bidentate directing group is reported. This strategy provided a regio- and stereoselective protocol for exclusive synthesis of Z-vinylsilanes with reasonable to excellent yields and good functional group compatibility. Silylation of the isolated palladacycle intermediate revealed the Z-stereoselective pathway. Moreover, the practicality and effectiveness of this method were illustrated by a gram-scale experiment and further functionalization of the silylation product.

An efficient and convenient method enabling direct amination of unactivated methylene C(sp 3 )−H bonds to form C−N bonds with azodiformates as amino source is described. This method highlights the emerging strategy of unactivated methylene as versatile functional groups in organic synthesis and provides a strategy to construct functionalized C−N bonds for the synthesis of complex molecules.

Asymmetric catalytic synthesis of 2,3-allenamides from hydrogen-bond-stabilized enynamides in the presence of quinine-based bifunctional squaramide organocatalysts is described. This protocol forms a variety of 2,3-allenamides in high yields and excellent stereoselectivities, in which the elaborated introduction of intramolecular H-bonds within the N,N-bidentate amide group constitutes one of the keys to this highly enantioselective transformation. The synthetic practicality of this reaction has been demonstrated by the axis-to-center chirality transfer of allenamides to furnish enantiomerically enriched building blocks.