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Broad-Scope Amination of Aryl Sulfamates Catalyzed by a Palladium Phosphine Complex.

ABSTRACT: Among phenol-derived electrophiles, aryl sulfamates are attractive substrates since they can be employed as directing groups for C-H functionalization prior to catalysis. However, their use in C-N coupling is limited only to Ni catalysis. Here, we describe a Pd-based catalyst with a broad scope for the amination of aryl sulfamates. We show that the N-methyl-2-aminobiphenyl palladacycle supported by the PCyp₂Ar^Xyl2 ligand (Cyp = cyclopentyl; Ar^Xyl2 = 2,6-bis(2,6-dimethylphenyl)phenyl) efficiently catalyzes the C-N coupling of aryl sulfamates with a variety of nitrogen nucleophiles, including anilines, primary and secondary alkyl amines, heteroaryl amines, N-heterocycles, and primary amides. DFT calculations support that the oxidative addition of the aryl sulfamate is the rate-determining step. The C-N coupling takes place through a cationic pathway in the polar protic medium.

SUBMITTER: Monti A

PROVIDER: S-EPMC10443792 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

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Broad-Scope Amination of Aryl Sulfamates Catalyzed by a Palladium Phosphine Complex.

Monti Andrea A López-Serrano Joaquín J Prieto Auxiliadora A Nicasio M Carmen MC

ACS catalysis 20230804 16

Among phenol-derived electrophiles, aryl sulfamates are attractive substrates since they can be employed as directing groups for C-H functionalization prior to catalysis. However, their use in C-N coupling is limited only to Ni catalysis. Here, we describe a Pd-based catalyst with a broad scope for the amination of aryl sulfamates. We show that the N-methyl-2-aminobiphenyl palladacycle supported by the PCyp2ArXyl2 ligand (Cyp = cyclopentyl; ArXyl2 = 2,6-bi ...[more]

PMID: 37614522

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