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Abstract A Brønsted acid catalyzed C–H functionalization of vinyldiazoacetates with 3-hydroxyisoindolinone is developed. This methodology provides a general access to E-substituted isoindolinone vinyldiazo compounds in good yields and excellent diastereoselectivities with broad substrate generality under mild conditions, and with 4-substituted 2-diazo-3-butenoates produces fused bicyclic pyrrolidines. The reaction generally involves addition of the N-acyl ketiminium electrophile, formed from the 3-hydroxyisoindolinone, to the vinylogous position of the vinyldiazo compound resulting in vinyldiazonium ion intermediates that undergo deprotonation to new vinyldiazo compounds or ring closure to fused bicyclic pyrrolidines. 

Triflimide catalysis of the [3 + 2]-cycloaddition of 3-indolymethanols with vinyldiazoacetates provides general access to β-tetrahydrocyclopenta[b]indol-substituted α-diazoesters. Initiated by addition of the in situ generated vinylogous iminium electrophile from 3-indolymethanol to the vinylogous position of the vinyldiazo compound and completed by intramolecular cyclization from the vinyldiazonium ion intermediate, this transformation occurs in good yields and excellent diastereoselectivity with a broad substrate scope under mild conditions. The resulting α-diazoesters undergo Rh2(OAc)4-catalyzed substrate-dependent 1,2-migration to form multisubstituted carbazoles in high yields. 

Highly selective formal [4 + 2]-cycloaddition of vinyldiazoacetates with azoalkenes from a-halohydrazones, as well as with cyclopentadiene and furan, occurs with light irradiation at room temperature, producing highly functionalized heterocyclic and bicyclic compounds in good yields and excellent diastereoseletivity. Under blue light these vinyldiazoacetate reagents selectively form unstable cyclopropenes that undergo intermolecular cycloaddition reactions at a faster rate than their competitive ene dimerization. [4 + 2]-cycloaddition of vinyldiazoacetates with in situ formed azoalkenes produces bicyclo[4.1.0]tetrahydropyridazine derivatives and, together with their cycloaddition using cyclopentadiene and furan that form tricyclic compounds, they occur with high chemoselectivity and diastereocontrol, good functional group tolerance, and excellent scalability. Subsequent transformations portray the synthetic versatility of these structures. 

N-heterocyclic carbene complexes of the typetrans-(NHC)₂Pt^II(CC–Ar)₂(where Ar = phenyl or substituted phenyl) are of interest as violet and blue phosphors. 

Diverse amines and amino acids are now readily accessed from carboxylic acids, aldehydes, and amine precursors in a direct decarboxylative reaction enabled by a homogeneous triple catalytic system based on acridine photocatalysis.