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Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination.
Acc Chem Res. 2015 Apr 21; 48(4):1040-52.AC

Abstract

Owing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon-nitrogen bonds. While metal-catalyzed C-N cross-coupling reactions have been established as one of the most general protocols for C-N bond formation, these methods require starting materials equipped with functional groups such as (hetero)aryl halides or their equivalents, thus generating stoichiometric amounts of halide salts as byproducts. To address this aspect, a transition-metal-catalyzed direct C-H amination approach has emerged as a step- and atom-economical alternative to the conventional C-N cross-coupling reactions. However, despite the significant recent advances in metal-mediated direct C-H amination reactions, most available procedures need harsh conditions requiring stoichiometric external oxidants. In this context, we were curious to see whether a transition-metal-catalyzed mild C-H amination protocol could be achieved using organic azides as the amino source. We envisaged that a dual role of organic azides as an environmentally benign amino source and also as an internal oxidant via N-N2 bond cleavage would be key to develop efficient C-H amination reactions employing azides. An additional advantage of this approach was anticipated: that a sole byproduct is molecular nitrogen (N2) under the perspective catalytic conditions. This Account mainly describes our research efforts on the development of rhodium- and iridium-catalyzed direct C-H amination reactions with organic azides. Under our initially optimized Rh(III)-catalyzed amination conditions, not only sulfonyl azides but also aryl- and alkyl azides could be utilized as facile amino sources in reaction with various types of C(sp(2))-H bonds bearing such directing groups as pyridine, amide, or ketoxime. More recently, a new catalyst system using Ir(III) species was developed for the direct C-H amidation of arenes and alkenes with acyl azides under exceptionally mild conditions. As a natural extension, amidation of primary C(sp(3))-H bonds could also be realized on the basis of the superior activity of the Cp*Ir(III) catalyst. Mechanistic investigations revealed that a catalytic cycle is operated mainly in three stages: (i) chelation-assisted metallacycle formation via C-H bond cleavage; (ii) C-N bond formation through the in situ generation of a metal-nitrenoid intermediate followed by the insertion of an imido moiety to the metal carbon bond; (iii) product release via protodemetalation with the concomitant catalyst regeneration. In addition, this Account also summarizes the recent advances in the ruthenium- and cobalt-catalyzed amination reactions using organic azides, developed by our own and other groups. Comparative studies on the relative performance of those catalytic systems are briefly described.

Authors+Show Affiliations

‡Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 305-338, Republic of Korea.‡Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 305-338, Republic of Korea.‡Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 305-338, Republic of Korea.

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

25821998

Citation

Shin, Kwangmin, et al. "Transition-metal-catalyzed C-N Bond Forming Reactions Using Organic Azides as the Nitrogen Source: a Journey for the Mild and Versatile C-H Amination." Accounts of Chemical Research, vol. 48, no. 4, 2015, pp. 1040-52.
Shin K, Kim H, Chang S. Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination. Acc Chem Res. 2015;48(4):1040-52.
Shin, K., Kim, H., & Chang, S. (2015). Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination. Accounts of Chemical Research, 48(4), 1040-52. https://doi.org/10.1021/acs.accounts.5b00020
Shin K, Kim H, Chang S. Transition-metal-catalyzed C-N Bond Forming Reactions Using Organic Azides as the Nitrogen Source: a Journey for the Mild and Versatile C-H Amination. Acc Chem Res. 2015 Apr 21;48(4):1040-52. PubMed PMID: 25821998.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Transition-metal-catalyzed C-N bond forming reactions using organic azides as the nitrogen source: a journey for the mild and versatile C-H amination. AU - Shin,Kwangmin, AU - Kim,Hyunwoo, AU - Chang,Sukbok, Y1 - 2015/03/30/ PY - 2015/3/31/entrez PY - 2015/3/31/pubmed PY - 2015/10/8/medline SP - 1040 EP - 52 JF - Accounts of chemical research JO - Acc Chem Res VL - 48 IS - 4 N2 - Owing to the prevalence of nitrogen-containing compounds in functional materials, natural products and important pharmaceutical agents, chemists have actively searched for the development of efficient and selective methodologies allowing for the facile construction of carbon-nitrogen bonds. While metal-catalyzed C-N cross-coupling reactions have been established as one of the most general protocols for C-N bond formation, these methods require starting materials equipped with functional groups such as (hetero)aryl halides or their equivalents, thus generating stoichiometric amounts of halide salts as byproducts. To address this aspect, a transition-metal-catalyzed direct C-H amination approach has emerged as a step- and atom-economical alternative to the conventional C-N cross-coupling reactions. However, despite the significant recent advances in metal-mediated direct C-H amination reactions, most available procedures need harsh conditions requiring stoichiometric external oxidants. In this context, we were curious to see whether a transition-metal-catalyzed mild C-H amination protocol could be achieved using organic azides as the amino source. We envisaged that a dual role of organic azides as an environmentally benign amino source and also as an internal oxidant via N-N2 bond cleavage would be key to develop efficient C-H amination reactions employing azides. An additional advantage of this approach was anticipated: that a sole byproduct is molecular nitrogen (N2) under the perspective catalytic conditions. This Account mainly describes our research efforts on the development of rhodium- and iridium-catalyzed direct C-H amination reactions with organic azides. Under our initially optimized Rh(III)-catalyzed amination conditions, not only sulfonyl azides but also aryl- and alkyl azides could be utilized as facile amino sources in reaction with various types of C(sp(2))-H bonds bearing such directing groups as pyridine, amide, or ketoxime. More recently, a new catalyst system using Ir(III) species was developed for the direct C-H amidation of arenes and alkenes with acyl azides under exceptionally mild conditions. As a natural extension, amidation of primary C(sp(3))-H bonds could also be realized on the basis of the superior activity of the Cp*Ir(III) catalyst. Mechanistic investigations revealed that a catalytic cycle is operated mainly in three stages: (i) chelation-assisted metallacycle formation via C-H bond cleavage; (ii) C-N bond formation through the in situ generation of a metal-nitrenoid intermediate followed by the insertion of an imido moiety to the metal carbon bond; (iii) product release via protodemetalation with the concomitant catalyst regeneration. In addition, this Account also summarizes the recent advances in the ruthenium- and cobalt-catalyzed amination reactions using organic azides, developed by our own and other groups. Comparative studies on the relative performance of those catalytic systems are briefly described. SN - 1520-4898 UR - https://www.unboundmedicine.com/medline/citation/25821998/Transition_metal_catalyzed_C_N_bond_forming_reactions_using_organic_azides_as_the_nitrogen_source:_a_journey_for_the_mild_and_versatile_C_H_amination_ L2 - https://doi.org/10.1021/acs.accounts.5b00020 DB - PRIME DP - Unbound Medicine ER -
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