Dehydrative Cross-Coupling for C-N Bond Construction under Transition-Metal-Free Conditions.

A transition-metal-free catalytic system was designed to address the dehydrative cross-coupling of unactivated primary/secondary alcohols with amines/amides under environmentally benign conditions. Mg2+ and counteranion (PF6-) worked synergistically to realize C-OH bond cleavage and concomitant C-N bond formation. A wide range of allylic alcohols and amines/amides were tolerated well in this transformation, which allowed C-N bond construction with high efficiency.

Dehydrative Allylation of Alkenyl sp2 C-H Bonds.

We designed a cooperative catalytic system by combining commercially available Ca(NTf2)PF6 and Pd(PPh3)4 to address the dehydrative allylation of alkenyl sp2 C-H bonds in an environmentally benign manner. A novel C-OH bond cleavage method was found to be crucial for this practical protocol. A variety of alkenes and allylic alcohols equipped with wide-spectrum functional groups can be successfully incorporated into the desired cross-coupling, affording 1,4-dienes with moderate to excellent yields and high stereo- and regioselectivity.