Synergistic palladium/enamine catalysis for asymmetric hydrocarbon functionalization of unactivated alkenes with ketones.

Synergistic palladium and enamine catalysis was explored to promote ketone addition to unactivated olefins. A secondary amine-based organocatalyst was identified as the optimal co-catalyst for the directed Pd-catalyzed alkene activation. Furthermore, asymmetric hydrocarbon functionalization of unactivated alkenes was also achieved with good to excellent yield (up to 96% yields) and stereoselectivity (up to 96% ee). This strategy presented an efficient approach to prepare α-branched ketone derivatives under mild conditions.

Direct functionalization of alkyl ethers to construct hemiaminal ether skeletons (HESs).

Hemiaminal ether skeletons (HESs) are important backbones generally found in organic compounds. Compared to traditional functional group transformations, strategies for the C-H functionalization of alkyl ethers to construct HESs have drawn much attention in the past decade. In this review, we focus on the recent progress in developing various pathways to construct HESs via the direct functionalization of alkyl ethers, including: (a) the transition-metal-catalyzed nitrene insertion pathway, (b) the transition-metal-free organonitrenoid insertion pathway,