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Copper-nitrenoid formation and transfer in catalytic olefin aziridination utilizing chelating 2-pyridylsulfonyl moieties.
J Org Chem. 2008 Apr 04; 73(7):2862-70.JO

Abstract

We have developed an efficient protocol for copper-catalyzed olefin aziridination using 5-methyl-2-pyridinesulfonamide or 2-pyridinesulfonyl azide as the nitrenoid source. The presence of a 2-pyridyl group significantly facilitates aziridination, suggesting that the reaction is driven by the favorable formation of a pyridyl-coordinated nitrenoid intermediate. Using this chelation-assisted strategy, synthetically acceptable yields of aziridines could be obtained with a range of aryl olefins even in the absence of external ligands. Importantly, a large excess of olefin is not required. X-ray crystallography, ESI-MS, Hammett plot analysis, kinetic studies, and computational undertakings strongly support that the observed aziridination is driven by internal coordination.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Han H
Center for Molecular Design and Synthesis, Department of Chemistry and School of Molecular Science (BK21), Korea Advanced Institute of Science and Technology, Daejon 305-701, Korea.
Park SB
No affiliation info available
Kim SK
No affiliation info available
Chang S
No affiliation info available

MeSH

AlkenesAziridinesCatalysisCopperCrystallography, X-RayIminesModels, MolecularMolecular StructureOrganometallic CompoundsPyridinesStereoisomerismSulfones

Pub Type(s)

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

Language

eng

PubMed ID

18327956

Citation

Han, Hoon, et al. "Copper-nitrenoid Formation and Transfer in Catalytic Olefin Aziridination Utilizing Chelating 2-pyridylsulfonyl Moieties." The Journal of Organic Chemistry, vol. 73, no. 7, 2008, pp. 2862-70.
Han H, Park SB, Kim SK, et al. Copper-nitrenoid formation and transfer in catalytic olefin aziridination utilizing chelating 2-pyridylsulfonyl moieties. J Org Chem. 2008;73(7):2862-70.
Han, H., Park, S. B., Kim, S. K., & Chang, S. (2008). Copper-nitrenoid formation and transfer in catalytic olefin aziridination utilizing chelating 2-pyridylsulfonyl moieties. The Journal of Organic Chemistry, 73(7), 2862-70. https://doi.org/10.1021/jo800134j
Han H, et al. Copper-nitrenoid Formation and Transfer in Catalytic Olefin Aziridination Utilizing Chelating 2-pyridylsulfonyl Moieties. J Org Chem. 2008 Apr 4;73(7):2862-70. PubMed PMID: 18327956.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Copper-nitrenoid formation and transfer in catalytic olefin aziridination utilizing chelating 2-pyridylsulfonyl moieties. AU - Han,Hoon, AU - Park,Seong Byeong, AU - Kim,Sang Kyu, AU - Chang,Sukbok, Y1 - 2008/03/08/ PY - 2008/3/11/pubmed PY - 2008/6/20/medline PY - 2008/3/11/entrez SP - 2862 EP - 70 JF - The Journal of organic chemistry JO - J Org Chem VL - 73 IS - 7 N2 - We have developed an efficient protocol for copper-catalyzed olefin aziridination using 5-methyl-2-pyridinesulfonamide or 2-pyridinesulfonyl azide as the nitrenoid source. The presence of a 2-pyridyl group significantly facilitates aziridination, suggesting that the reaction is driven by the favorable formation of a pyridyl-coordinated nitrenoid intermediate. Using this chelation-assisted strategy, synthetically acceptable yields of aziridines could be obtained with a range of aryl olefins even in the absence of external ligands. Importantly, a large excess of olefin is not required. X-ray crystallography, ESI-MS, Hammett plot analysis, kinetic studies, and computational undertakings strongly support that the observed aziridination is driven by internal coordination. SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/18327956/Copper_nitrenoid_formation_and_transfer_in_catalytic_olefin_aziridination_utilizing_chelating_2_pyridylsulfonyl_moieties_ DB - PRIME DP - Unbound Medicine ER -