Palladium(II)-Catalyzed Enantioselective Ring Opening of Oxabenzonorbornadienes via Domino Aminopalladation of Alkynylanilines.

We report herein a robust enantioselective ring opening coupling of oxabenzonorbornadienes via Pd(II)-catalyzed domino cyclization of alkynylanilines, which features the formation of three covalent bonds and two contiguous stereocenters with excellent enantio- and diastereoselectivity and a broad substrate scope. The good functional group tolerance of this domino desymmetrization strategy enables efficient late-stage transformation of natural product-derived alkynylanilines. The resulting indolated dihydronaphthols could serve as a valuable platform to streamline the diversity-oriented synthesis of other valuable enantioenriched tetrahydronaphthalene derivatives.

Synergistic Pd/Ni Dual-Catalyzed Cross-Coupling of Azaaryl Acetates with -Difluorinated Cyclopropanes.

We herein report the development of a novel Pd/Ni dual-catalyzed ring-opening functionalization of -difluorinated cyclopropanes (-FCPs) with azaaryl acetates. This bimetallic catalytic strategy streamlines the diversity-oriented synthesis (DOS) of α-quaternary 2-fluoroallylic azaaryl acetates with features of a broad scope and excellent functional group tolerance, which enables the efficient late-stage transformation of natural product-derived -FCPs. The resulting α-quaternary azaaryl acetates could serve as a valuable platform to prepare other different fluoroallylic azaaryl scaffolds.

Palladium/Amine Dual-Catalyzed Tsuji-Trost Fluoroallylation of Aldehydes with -Difluorinated Cyclopropanes.

We herein disclose the Pd/amine dual-catalyzed ring-opening cross-coupling reaction between -difluorinated cyclopropanes (-FCPs) with aldehydes, which enables the diversity-oriented synthesis (DOS) of 2-fluoroallylic aldehydes bearing all-carbon quaternary centers with features of broad scope and excellent functional group tolerance. The synthetic value of this Tsuji-Trost system was further demonstrated by late-stage functionalization of natural product-derived -FCPs and the diverse synthesis of various fluoroallylic aldehyde derivatives, including alcohol, alkyne, alkene, and amine.

Enantioselective Tsuji-Trost α-Fluoroallylation of Amino Acid Esters with Gem-Difluorinated Cyclopropanes.

A novel enantioselective Tsuji-Trost-type cross coupling reaction between gem-difluorinated cyclopropanes and N-unprotected amino acid esters enabled by synergistic Pd/Ni/chiral aldehyde catalysis is presented herein. This transformation streamlined the diversity-oriented synthesis (DOS) of optically active α-quaternary α-amino acid esters bearing a linear 2-fluoroallylic motif, which served as an appealing platform for the construction of other valuable enantioenriched compounds. The key intermediates were confirmed by HRMS detection, while DFT calculations revealed that the excellent enantioselectivity was attributed to the stabilizing non-covalent interactions between the Pd(II)-π-fluoroallyl species and the Ni(II)-Schiff base complex.