Regiodivergent Metal-Catalyzed Rearrangement of 3-Iminocyclopropenes into N-Fused Heterocycles

A highly efficient regiodivergent method for the synthesis of N-fused heterocycles via transition-metal-catalyzed rearrangement of 3-iminocyclopropenes has been developed

Can Agostic Interaction Affect Regiochemistry of Carbopalladation? Reverse Regioselectivity in the Palladium-Catalyzed Dimerization of Aryl Acetylenes

Can Agostic Interaction Affect Regiochemistry of Carbopalladation? Reverse Regioselectivity in the Palladium-Catalyzed Dimerization of Aryl Acetylene

Sila-Morita−Baylis−Hillman Reaction of Arylvinyl Ketones: Overcoming the Dimerization Problem

Arylvinyl ketones, under Morita−Baylis−Hillman (MBH) reaction conditions, produce a mixture of dimerization products. We propose a solution to this problem: a sila-MBH reaction. This cascade reaction involves addition of phosphine catalyst to arylvinyl ketones, trapping of the forming β-silylenolate with aldehyde, followed by a 1,3-Brook rearrangement to give the Si-MBH adducts in good to excellent yields

Rhodium Thiavinyl Carbenes from 1,2,3-Thiadiazoles Enable Modular Synthesis of Multisubstituted Thiophenes

The rhodium-catalyzed transannulation reaction between 1,2,3-thiadiazoles and alkynes, proceeding via intermediacy of the previously unknown Rh thiavinyl carbene, toward a highly efficient and regioselective synthesis of up to fully substituted thiophenes is described

Palladium-Catalyzed Intramolecular Carbopalladation/Cyclization Cascade: Access to Polycyclic N-Fused Heterocycles

An efficient palladium-catalyzed intramolecular carbopalladation/cyclization cascade toward tetra- and pentacyclic N-fused heterocycles has been developed. This transformation proceeds via the palladium-catalyzed coupling of aryl halides with internal propargylic esters or ethers followed by the 5-endo-dig cyclization leading to polycyclic pyrroloheterocycles in moderate to excellent yields

B(C₆F₅)₃-Catalyzed Allylation of Secondary Benzyl Acetates with Allylsilanes

A highly effective protocol for allylation of secondary benzylic alcohol derivatives with allylsilanes in the presence of catalytic amounts of B(C6F5)3 has been developed. Some additional functionalities, such as bromo, acetoxy, and primary benzyloxy groups, were tolerated under these conditions

General and Practical One-Pot Synthesis of Dihydrobenzosiloles from Styrenes

A one-pot synthesis of dihydrobenzosiloles from styrenes has been developed. The reaction involves the nickel-catalyzed hydrosilylation of styrene with diphenylsilane, followed by the iridium-catalyzed dehydrogenative cyclization. This method is efficient for both electron-rich and -deficient styrenes and exhibits good functional group tolerance, as well as excellent regioselectivity. The forming dihydrobenzosiloles can be efficiently converted into valuable benzosiloles or 2-hydroxyphenethyl alcohols

Intramolecular Transannulation of Alkynyl Triazoles via Alkyne–Carbene Metathesis Step: Access to Fused Pyrroles

An intramolecular Rh-catalyzed transannulation reaction of alkynyl triazoles has been developed. This method allows efficient construction of various 5,5-fused pyrroles, including tetrahydropyrrolo and spiro systems. The method demonstrates excellent functional group compatibility. A rhodium carbene–alkyne metathesis mechanism is proposed for this transformation

Exclusive 5-<i>exo-dig</i> Hydroarylation of <i>o</i>-Alkynyl Biaryls Proceeding via C−H Activation Pathway

Exclusive 5-exo-dig Hydroarylation of o-Alkynyl Biaryls Proceeding via C−H Activation Pathwa

Palladium Hydride-Enabled Hydroalkenylation of Strained Molecules

We report the first palladium hydride enabled hydroalkenylation of strained molecules. This new mild protocol proceeds via a regio- and chemoselective hydropalladation step, followed by a photoinduced radical alkyl Heck reaction. This methodology represents a new reactivity mode for strained molecules and opens new avenues for photoinduced palladium catalysis. The reaction is compatible with a wide range of functional groups and can be applied to complex structures, delivering a diverse array of highly valuable and modifiable alkenylated cyclobutanes and cyclopropanes. A hydroalkenylation/diastereoselective rearrangement cascade toward a cyclopentene scaffold has also been demonstrated