Oxidative Amidation of Activated Alkenes Using Pd(OAc)2 as a Catalyst Precursor

• Published in: European Journal of Organic Chemistry Vol. 2010; no. 27; pp. 5181 - 5189
• Main Authors: Liu, Xinzhu, Hii, King Kuok (Mimi)
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.09.2010; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: Alkenes; Amides; Catalysis; Catalysts: preparations and properties; Chemistry; Chemistry, Organic; Enamines; Exact sciences and technology; General and physical chemistry; Heterocyclic compounds; Heterocyclic compounds with n hetero atom and also o and/or s, se, te hetero atoms; Homogeneous catalysis; Organic chemistry; Palladium; Physical Sciences; Preparations and properties; Science & Technology; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; AMINATION; ACID; Alkenes; AMINES; Homogeneous catalysis; Amides; OLEFINS; Palladium; Enamines; Enamine; Saturated compound; Palladium complex; Selectivity; Primary amide; Oxidant; Organic carbamate; Hydrogenation; Amidation; Alkene; Steric effect; Oxidation; Copper; Palladium II Acetate; Oxygen nitrogen heterocycle; Transition metal; Air; Copper II Acetate; Olefin; Cyclic compound; Oxazolidinone derivative; Carboxamide; Pyrrolidone derivatives; Catalyst activity; Catalyst; Ethylenic compound; Nucleophile
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201000384

A new “chloride‐free” protocol was developed for oxidative amidation reactions between cyclic and acyclic amides and carbamates with activated olefins, conducted under Pd/Cu catalysis, using air as a terminal oxidant. The presence of TsOH is important for catalytic activity. The scope of the reaction includes the addition of primary amides, carbamates, as well as cyclic oxazolidinone and pyrrolidinone. The reactions are found to be sensitive to steric demand of the N‐nucleophile, and E‐selectivity can be achieved exclusively with cyclic N‐nucleophiles. The products can be easily hydrogenated to afford the saturated product in high yields. A new “chloride‐free” protocol was developed for oxidative amidation reactions between cyclic and acyclic amides and carbamates with electron‐deficient olefins, conducted under Pd/Cu catalysis, using air as oxidant. The products can be easily hydrogenated to afford the saturated products in high yields.