Pd-Catalyzed 1,4-Carboamination of Bicyclic Bromoarenes with Diazo Compounds and Amines

Abstract

A palladium-catalyzed 1,4-carboamination of bromoarenes with diazo compounds and amines was developed. This reaction proceeds through a palladium-carbene that then generates a π-benzylpalladium intermediate, forming ipso C–C and para C–N bonds on bromoarenes in a regioselective manner. The successful application of this transformation to the rapid synthesis of an antitumor agent demonstrates its synthetic utility.

Palladium hydrazonato complexes and their role in the Pd-catalyzed cross-coupling reactions of hydrazones as carbene precursors

“…N -Tosylhydrazone derivatives R′SO 2 NHNCHR (R = CHCHPh ( 3 ), Ph ( 4 ); R′ = Tol, Ph) were tested, since they are common reactants in many Pd-catalyzed processes. 2 d ,10,11 Additionally, the reactivity of complexes 2 with the analogous diazocompounds N 2 CHR, which can be formed in basic media from the hydrazones, has been previously studied and therefore any product resulting from the in situ formed diazoalkanes can be detected. 12…”

Palladium-Catalyzed para-Selective Allylation of 1-(Cyanomethyl)arenes with Allyl Acetates

“…The use of alternative alkyl- or alkylphenylphosphines of varying steric bulk and Lewis basicity resulted in the decreased yields of 3a and lower selectivity due to appreciable diallylation (entries 2–6). DPPF, DPPB, and PPh 2 (C 6 H 4 - p -NMe 2 ), previously shown to be effective ligands for the Pd-catalyzed dearomative para -allylation of benzyl electrophiles, ,, were less efficient than PMe 3 (entries 7–10). Accordingly, given the superiority of PMe 3 , we optimized the PMe 3 content of catalytic mixtures.…”

Diazo compounds and palladium–aryl complexes: trapping the elusive carbene migratory insertion organometallic products

“…15 The formation of complex 6 supports the intermediacy of benzylic palladium derivatives in catalytic coupling reactions of phenyldiazomethane derivatives, as has been suggested before. 13…”