Highly selective olefin-assisted palladium-catalyzed oxidative carbocyclization via remote olefin insertion† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc02660e

Palladium-catalyzed cross-coupling of α-bromocarbonyls and allylic alcohols for the synthesis of α-aryl dicarbonyl compounds† †Electronic supplementary information (ESI) available. CCDC 1042318. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00505a

The palladium-catalyzed coupling of olefins and organohalides is a versatile approach for synthesizing complex molecules from simple starting materials. We have developed a palladium-catalyzed coupling of α-bromocarbonyl compounds with allylic alcohols for the generation of acyclic aryl-substituted dicarbonyl compounds. The reaction proceeds via a tandem olefin insertion of an α-acyl radical fo...

Highly Efficient Cascade Reaction for Selective Formation of Spirocyclobutenes from Dienallenes via Palladium-Catalyzed Oxidative Double Carbocyclization–Carbonylation–Alkynylation

A highly selective cascade reaction that allows the direct transformation of dienallenes to spirocyclobutenes (spiro[3.4]octenes) as single isomers has been developed. The reaction involves formation of overall four C-C bonds and proceeds via a palladium-catalyzed oxidative transformation with insertion of olefin, olefin, and carbon monoxide. Under slightly different reaction conditions an addi...

Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling† †Electronic supplementary information (ESI) available: Experimental details. See DOI: 10.1039/c7sc04207h

Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in eithe...

Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation† †Electronic supplementary information (ESI) available: Materials and methods, reaction procedures, characterization data. CCDC 1056687, 1062118. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01553g Click here for additional data file. Click here for additional data file.

We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C-H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopen...

Oxalyl amide assisted palladium-catalyzed synthesis of pyrrolidones via carbonylation of γ-C(sp3)–H bonds of aliphatic amine substrates† †Electronic supplementary information (ESI) available: Experimental procedures, characterization data for all new compounds. CCDC 1048649. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00519a