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Asymmetric nitrene transfer reactions: sulfimidation, aziridination and C-H amination using azide compounds as nitrene precursors.
Chem Rec. 2014 Feb; 14(1):117-29.CR

Abstract

Nitrogen functional groups are found in many biologically active compounds and their stereochemistry has a profound effect on biological activity. Nitrene transfer reactions such as aziridination, C-H bond amination, and sulfimidation are useful methods for introducing nitrogen functional groups, and the enantiocontrol of the reactions has been extensively investigated. Although high enantioselectivity has been achieved, most of the reactions use (N-arylsulfonylimino)phenyliodinane, which co-produces iodobenzene, as a nitrene precursor and have a low atom economy. Azide compounds, which give nitrene species by releasing nitrogen, are ideal precursors but rather stable. Their decomposition needs UV irradiation, heating in the presence of a metal complex, or Lewis acid treatment. The examples of previous azide decomposition prompted us to examine Lewis acid and low-valent transition-metal complexes as catalysts for azide decomposition. Thus, we designed new ruthenium complexes that are composed of a low-valent Ru(II) ion, apical CO ligand, and an asymmetry-inducing salen ligand. With these ruthenium complexes and azides, we have achieved highly enantioselective nitrene transfer reactions under mild conditions. Recently, iridium-salen complexes were added to our toolbox.

Authors+Show Affiliations

Faculty of Arts and Science, Kyushu University, Hakozaki, Higashi-ku, Fukuoka, 812-8581, Japan; International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Hakozaki, Higashi-ku, Fukuoka, 812-8581, Japan.No affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

24449500

Citation

Uchida, Tatsuya, and Tsutomu Katsuki. "Asymmetric Nitrene Transfer Reactions: Sulfimidation, Aziridination and C-H Amination Using Azide Compounds as Nitrene Precursors." Chemical Record (New York, N.Y.), vol. 14, no. 1, 2014, pp. 117-29.
Uchida T, Katsuki T. Asymmetric nitrene transfer reactions: sulfimidation, aziridination and C-H amination using azide compounds as nitrene precursors. Chem Rec. 2014;14(1):117-29.
Uchida, T., & Katsuki, T. (2014). Asymmetric nitrene transfer reactions: sulfimidation, aziridination and C-H amination using azide compounds as nitrene precursors. Chemical Record (New York, N.Y.), 14(1), 117-29. https://doi.org/10.1002/tcr.201300027
Uchida T, Katsuki T. Asymmetric Nitrene Transfer Reactions: Sulfimidation, Aziridination and C-H Amination Using Azide Compounds as Nitrene Precursors. Chem Rec. 2014;14(1):117-29. PubMed PMID: 24449500.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Asymmetric nitrene transfer reactions: sulfimidation, aziridination and C-H amination using azide compounds as nitrene precursors. AU - Uchida,Tatsuya, AU - Katsuki,Tsutomu, Y1 - 2014/01/22/ PY - 2013/09/13/received PY - 2014/1/23/entrez PY - 2014/1/23/pubmed PY - 2014/1/23/medline KW - amination KW - asymmetric catalysis KW - azides KW - nitrenes KW - ruthenium SP - 117 EP - 29 JF - Chemical record (New York, N.Y.) JO - Chem Rec VL - 14 IS - 1 N2 - Nitrogen functional groups are found in many biologically active compounds and their stereochemistry has a profound effect on biological activity. Nitrene transfer reactions such as aziridination, C-H bond amination, and sulfimidation are useful methods for introducing nitrogen functional groups, and the enantiocontrol of the reactions has been extensively investigated. Although high enantioselectivity has been achieved, most of the reactions use (N-arylsulfonylimino)phenyliodinane, which co-produces iodobenzene, as a nitrene precursor and have a low atom economy. Azide compounds, which give nitrene species by releasing nitrogen, are ideal precursors but rather stable. Their decomposition needs UV irradiation, heating in the presence of a metal complex, or Lewis acid treatment. The examples of previous azide decomposition prompted us to examine Lewis acid and low-valent transition-metal complexes as catalysts for azide decomposition. Thus, we designed new ruthenium complexes that are composed of a low-valent Ru(II) ion, apical CO ligand, and an asymmetry-inducing salen ligand. With these ruthenium complexes and azides, we have achieved highly enantioselective nitrene transfer reactions under mild conditions. Recently, iridium-salen complexes were added to our toolbox. SN - 1528-0691 UR - https://www.unboundmedicine.com/medline/citation/24449500/Asymmetric_nitrene_transfer_reactions:_sulfimidation_aziridination_and_C_H_amination_using_azide_compounds_as_nitrene_precursors_ L2 - https://doi.org/10.1002/tcr.201300027 DB - PRIME DP - Unbound Medicine ER -
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