Hydrazines and Azides via the Metal-Catalyzed Hydrohydrazination and Hydroazidation of Olefins

• Published in: Journal of the American Chemical Society Vol. 128; no. 35; pp. 11693 - 11712
• Main Authors: Waser, Jérôme, Gaspar, Boris, Nambu, Hisanori, Carreira, Erick M
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 06.09.2006; Amer Chemical Soc
• Subjects: Alkenes - chemistry; Azides - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; Cobalt - chemistry; Exact sciences and technology; General and physical chemistry; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Hydrazines - chemistry; Kinetics and mechanisms; Manganese - chemistry; Models, Chemical; Molecular Structure; Organic chemistry; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; CLICK CHEMISTRY APPROACH; INTERMOLECULAR HYDROAMINATION; INTRAMOLECULAR HYDROAMINATION; ANTI-MARKOVNIKOV HYDROAMINATION; ALPHA-AMINO-ACIDS; ALPHA,BETA-UNSATURATED CARBONYL-COMPOUNDS; ELECTROPHILIC AMINATION; HUISGEN 1,3-DIPOLAR CYCLOADDITION; OXIDATION-REDUCTION HYDRATION; MOLECULAR-OXYGEN; Catalytic reaction; Transition element complexes; Sulfone; Organic azide; Nitrogen heterocycle; Organic silane; Reaction rate; Characterization; Alkene; Amine; Olefin; Amination; Functionalization; Organic free radical; Manganese Carbonyl Complexes; Reaction mechanism; Triazole derivatives; Isolation; Oxidation; Hydrazine; Protection; Ethylenic compound; Functional group
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja062355+

The discovery, study, and implementation of the Co- and Mn-catalyzed hydrohydrazination and hydroazidation reactions of olefins are reported. These reactions are equivalent to direct hydroaminations of C−C double bonds with protected hydrazines or hydrazoic acid but are based on a different concept in which the H and the N atoms come from two different reagents, a silane and an oxidizing nitrogen source (azodicarboxylate or sulfonyl azide). The hydrohydrazination reaction using di-tert-butyl azodicarboxylate is characterized by its ease of use, large functional group tolerance, and broad scope, including mono-, di-, tri-, and tetrasubstituted olefins. Key to the development of the hydroazidation reaction was the use of sulfonyl azides as nitrogen sources and the activating effect of tert-butyl hydroperoxide. The reaction was found to be efficient for the functionalization of mono-, di-, and trisubstituted olefins, and only a few functional groups are not tolerated. The alkyl azides obtained are versatile intermediates and can be transformed to the free amines or triazoles without isolation of the azides. Preliminary mechanistic investigations suggest a rate-limiting hydrocobaltation of the alkene, followed by an amination reaction. Radical intermediates cannot be ruled out and may be involved.