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Volumn 14, Issue 20, 2008, Pages 6222-6230

N-tosyloxycarbamates as reagents in rhodium-catalyzed C-H amination reactions

Author keywords

Amination; Carbamates; Catalysis; Insertion; Rhodium

Indexed keywords

AMINES; NITROGEN COMPOUNDS; ORGANIC COMPOUNDS; POROUS MATERIALS; POTASSIUM; RHODIUM; RHODIUM COMPOUNDS;

EID: 53849147524     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200702027     Document Type: Article
Times cited : (150)

References (94)
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    • Intramolecular C-H insertions lead to 5-membered rings with carbamates and to 6-membered rings with sulfamates.
    • Intramolecular C-H insertions lead to 5-membered rings with carbamates and to 6-membered rings with sulfamates.
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    • TGA has shown that 12 is stable at temperatures as high as 180°C.
    • TGA has shown that 12 is stable at temperatures as high as 180°C.
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    • Interestingly, this side chain was also the best nitrene precursor for reactions of sulfonamides in the presence of a rhodium dimer and (diacetoxyiodo)benzene (see Ref. [9r]). Clearly, in both reactions it is important to have a metal nitrene with an electron-withdrawing substituent for efficient C-H insertion.
    • Interestingly, this side chain was also the best nitrene precursor for reactions of sulfonamides in the presence of a rhodium dimer and (diacetoxyiodo)benzene (see Ref. [9r]). Clearly, in both reactions it is important to have a metal nitrene with an electron-withdrawing substituent for efficient C-H insertion.
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    • Such cyclopropane derivatives have been used previously by Fiori and Du Bois as radical clock substrates; see Ref, 9r] for details
    • Such cyclopropane derivatives have been used previously by Fiori and Du Bois as radical clock substrates; see Ref. [9r] for details.
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    • This data was not included in the Hammett analysis because k At/kPh lends towards 0
    • Ph lends towards 0.
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    • A comparison between rhodium carbamate and sulfamate nitrene is difficult to establish because the role of the hypervalent iodine reagent (which is only present for the generation of sulfamate nitrene) is not fully understood and could interfere with the kinetic of the reaction; J. Du Bois, personal communication; see also Ref. [9r].
    • A comparison between rhodium carbamate and sulfamate nitrene is difficult to establish because the role of the hypervalent iodine reagent (which is only present for the generation of sulfamate nitrene) is not fully understood and could interfere with the kinetic of the reaction; J. Du Bois, personal communication; see also Ref. [9r].
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    • Pyridine was added to completely liberate the product from the catalyst
    • Pyridine was added to completely liberate the product from the catalyst.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.