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Mechanistic studies of the rhodium-catalyzed direct C-H amination reaction using azides as the nitrogen source.
J Am Chem Soc. 2014 Feb 12; 136(6):2492-502.JA

Abstract

Direct C-H amination of arenes offers a straightforward route to aniline compounds without necessitating aryl (pseudo)halides as the starting materials. The recent development in this area, in particular in the metal-mediated transformations, is significant with regard to substrate scope and reaction conditions. Described herein are the mechanistic details on the Rh-catalyzed direct C-H amination reaction using organic azides as the amino source. The most important two stages were investigated especially in detail: (i) the formation of metal nitrenoid species and its subsequent insertion into a rhodacycle intermediate, and (ii) the regeneration of catalyst with concomitant release of products. It was revealed that a stepwise pathway involving a key Rh(V)-nitrenoid species that subsequently undergoes amido insertion is favored over a concerted C-N bond formation pathway. DFT calculations and kinetic studies suggest that the rate-limiting step in the current C-H amination reaction is more closely related to the formation of Rh-nitrenoid intermediate rather than the presupposed C-H activation process. The present study provides mechanistic details of the direct C-H amination reaction, which bears both aspects of the inner- and outer-sphere paths within a catalytic cycle.

Authors+Show Affiliations

Center for Catalytic Hydrocarbon Functionalizations, Institute of Basic Science (IBS) , Daejeon 305-701, Republic of Korea.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

24450395

Citation

Park, Sae Hume, et al. "Mechanistic Studies of the Rhodium-catalyzed Direct C-H Amination Reaction Using Azides as the Nitrogen Source." Journal of the American Chemical Society, vol. 136, no. 6, 2014, pp. 2492-502.
Park SH, Kwak J, Shin K, et al. Mechanistic studies of the rhodium-catalyzed direct C-H amination reaction using azides as the nitrogen source. J Am Chem Soc. 2014;136(6):2492-502.
Park, S. H., Kwak, J., Shin, K., Ryu, J., Park, Y., & Chang, S. (2014). Mechanistic studies of the rhodium-catalyzed direct C-H amination reaction using azides as the nitrogen source. Journal of the American Chemical Society, 136(6), 2492-502. https://doi.org/10.1021/ja411072a
Park SH, et al. Mechanistic Studies of the Rhodium-catalyzed Direct C-H Amination Reaction Using Azides as the Nitrogen Source. J Am Chem Soc. 2014 Feb 12;136(6):2492-502. PubMed PMID: 24450395.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Mechanistic studies of the rhodium-catalyzed direct C-H amination reaction using azides as the nitrogen source. AU - Park,Sae Hume, AU - Kwak,Jaesung, AU - Shin,Kwangmin, AU - Ryu,Jaeyune, AU - Park,Yoonsu, AU - Chang,Sukbok, Y1 - 2014/01/30/ PY - 2014/1/24/entrez PY - 2014/1/24/pubmed PY - 2014/1/24/medline SP - 2492 EP - 502 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 136 IS - 6 N2 - Direct C-H amination of arenes offers a straightforward route to aniline compounds without necessitating aryl (pseudo)halides as the starting materials. The recent development in this area, in particular in the metal-mediated transformations, is significant with regard to substrate scope and reaction conditions. Described herein are the mechanistic details on the Rh-catalyzed direct C-H amination reaction using organic azides as the amino source. The most important two stages were investigated especially in detail: (i) the formation of metal nitrenoid species and its subsequent insertion into a rhodacycle intermediate, and (ii) the regeneration of catalyst with concomitant release of products. It was revealed that a stepwise pathway involving a key Rh(V)-nitrenoid species that subsequently undergoes amido insertion is favored over a concerted C-N bond formation pathway. DFT calculations and kinetic studies suggest that the rate-limiting step in the current C-H amination reaction is more closely related to the formation of Rh-nitrenoid intermediate rather than the presupposed C-H activation process. The present study provides mechanistic details of the direct C-H amination reaction, which bears both aspects of the inner- and outer-sphere paths within a catalytic cycle. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/24450395/Mechanistic_studies_of_the_rhodium_catalyzed_direct_C_H_amination_reaction_using_azides_as_the_nitrogen_source_ L2 - https://doi.org/10.1021/ja411072a DB - PRIME DP - Unbound Medicine ER -
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