Iridium(III)-Catalyzed C-H Cyclization of Sulfoximines with Diazo Meldrum's Acids for the Synthesis of Cyclic Sulfoximines.

Iridium(III)-catalyzed C-H cyclization of sulfoximines with diazo Meldrum's acid provided cyclic sulfoximines with a carbonyl group in good to excellent yields. These compounds were easily converted into unsubstituted and arylated sulfoximines. Moreover, the vinyl triflates obtained from the cyclic sulfoximines underwent palladium(II)-catalyzed cross-coupling reactions with a variety of aryl, arylalkynyl, and heteroatom (N and S) nucleophiles, affording a wide range of monosubstituted sulfoximines in high yields.

Synthesis of o-Carborane-Fused Pyrazoles through Sequential C-N Bond Formation.

Transition-metal-free synthetic method for o-carborane-fused pyrazoles as a new scaffold has been developed from the reaction of B(4)-acylmethyl or B(3,5)-diacylmethyl o-carborane with 2-azido-1,3-dimethylimidazolinium hexafluorophosphate (ADMP) in the presence of DBU in acetonitrile through sequential diazotization and cyclization reaction in one pot, consequently allowing twofold C-N bond formation under extremely mild conditions and high functional group tolerance.

Iridium(III)-Catalyzed Regioselective B(4)-H Allenylation of o-Carboranes by Ball Milling.

We disclose an iridium(III)-catalyzed regioselective B(4)-H allenylation of o-carboranes from o-carborane acids and propargyl carbonates under ball-milling conditions. This study sheds light on a novel method to accomplish regioselective B(4)-allenylation of o-carborane that cannot be realized through conventional solution-based reactions. Control experiments, including solution, neat, microwave, and high-temperature reactions, reveal that the B(4)-H allenylation of o-carborane is unique for ball-milling conditions.

Rhodium-Catalyzed B(4)-H and B(3)-H Alkylation Reaction of Pyridyl o-Carboranes with α-Diazodicarboxylates.

An efficient Rh-catalyzed B(4)-H and B(3)-H alkylation reaction was demonstrated from the reactions of a variety of pyridyl o-carboranes with α-diazodicarboxylates with the release of molecular nitrogen, leading to the production of B(4)-H and B(3)-H alkylated o-carboranes in good to excellent yields with high selectivity, a wide substrate scope, and good functional group tolerance.

Iridium(III)-Catalyzed B(4)-Acylmethylation and B(3,5)-Diacylmethylation from o-Carboranes and Sulfoxonium Ylides.

An iridium(III)-catalyzed regioselective acylmethylation of the cage B(4)-H bond in o-carborane acids with sulfoxonium ylides is demonstrated through B(4)-H activation in ethanol under very mild conditions, affording a number of B(4)-acylmethylated o-carboranes. Additionally, the selective sequential B(4)- and B(6)-acylmethylation reactions finally gave B(3,5)-diacylmethylated o-carboranes in one pot.

Direct and Regioselective Palladium(II)-Catalyzed B(4)-H Monoacyloxylation and B(4,5)-H Diacetoxylation of o-Carborane Acids with Phenyliodonium Dicarboxylates.

A direct B(4)-H monoacyloxylation via a Pd-catalyzed regioselective B(4)-H activation of o-carborane acids with phenyliodonium dicarboxylates was developed, and a series of B(4)-H monoacyloxylated o-carboranes decorated with active groups were synthesized with moderate to good yields as well as excellent selectivity. In addition, a direct B(4,5)-H diacetoxylation from o-carborane acids with phenyliodonium diacetate was demonstrated.

Rhodium(III)-Catalyzed Sequential C-H Activation and Cyclization from N-Methoxyarylamides and 3-Diazooxindoles for the Synthesis of Isochromenoindolones.

An efficient synthetic method for structurally various isochromenoindolones has been demonstrated through Rh(III)-catalyzed C-H activation followed by a cyclization reaction of N-methoxyarylamides with 3-diazooxindoles. The sequential reaction involves the streamlined formation of C-C and C-O bonds in one pot. The present method provides a broad range of isochromenoindolones as a new privileged scaffold in moderate to good yields with the release of methoxyamine and molecular nitrogen and has the benefits of a broad substrate scope and good functional group tolerance.

Iridium-Catalyzed Cyclative Indenylation and Dienylation through Sequential B(4)-C Bond Formation, Cyclization, and Elimination from o-Carboranes and Propargyl Alcohols.

Described herein is the first iridium-catalyzed cyclative indenylation through sequential B(4)-C and intramolecular C-C bond formation from o-carboranes and propargyl alcohols, leading to the formation of B(4)-indenylated o-carboranes with excellent regioselectivity via direct B-H activation. Moreover, the iridium-catalyzed regioselective 1,3-dienylation has been accessed through sequential B-H activation, dehydration, and decarboxylation, producing B(4)-dienylated o-carboranes.

Expansion of Azulenes as Nonbenzenoid Aromatic Compounds for C-H Activation: Rhodium- and Iridium-Catalyzed Oxidative Cyclization of Azulene Carboxylic Acids with Alkynes for the Synthesis of Azulenolactones and Benzoazulenes.

Rhodium-catalyzed oxidative [4 + 2] cyclization reactions through the C-H activation of azulene carboxylic acids as nonbenzenoid aromatic compounds with symmetrical and unsymmetrical alkynes were developed under aerobic conditions, which produced azulenolactone derivatives with a wide substrate scope and excellent functional group tolerance. Interestingly, azulenic acids in reaction with alkynes underwent iridium-catalyzed [2 + 2 + 2] cyclization accompanied by decarboxylation to afford tetra(aryl)-substituted benzoazulene derivatives. The reactivity order for C-H activation reaction is greater toward azulene-6-carboxylic acid, azulene-1-carboxylic acid, and azulene-2-carboxylic acid. For the first time, the expansion of azulenes having directing group as nonbenzenoid aromatic compounds for C-H activation was successful, indicating that nonbenzenoid aromatic compounds can be used as good substrates for the C-H activation reaction. Therefore, the research area of C-H activation will certainly expand to nonbenzenoid aromatic compounds in future.