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Volumn 16, Issue 8, 2010, Pages 2619-2627

Tertiary carbinamine synthesis by rhodium-catalyzed [3+2] annulation of N-Unsubstituted aromatic ketimines and alkynes

Author keywords

Alkynes; C H activation; Carbinamines; Ketimines; Rhodium

Indexed keywords

ALKENYL; ALKYNE INSERTIONS; C-H ACTIVATION; CARBINAMINES; CATALYTIC CYCLES; CH-BOND ACTIVATION; GOOD YIELD; HIGH SELECTIVITY; INTERNAL ALKYNES; ISOQUINOLINES; KETIMINES; OPTIMIZED CONDITIONS; RHODIUM-CATALYZED;

EID: 77049085777     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200902814     Document Type: Article
Times cited : (145)

References (93)
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    • nM-X") to intermediate A is shown in Scheme 1 as a single step, generating one equivalent of HX. Such a one-step process is often used to describe an electrophilic substitution pathway for C-H bond activation. However, we would like to clarify that the current one-step transformation is a simplified description and does not imply an electrophilic substitution pathway (see the Results and Discussion for details).
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    • It is likely that the low yields resulted from competitive pathways mediated by rhodium hydride species. However, attempted reactions with various added hydrogen acceptors did not give improved yields
    • It is likely that the low yields resulted from competitive pathways mediated by rhodium hydride species. However, attempted reactions with various added hydrogen acceptors did not give improved yields.
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    • It is likely that terminal alkynes formed unproductive rhodium-alkynyl complexes, although detection of such species was not attempted. The lack of reactivity of trialkylsilyl-substituted alkynes could result from the steric hindrance or electronic effects from the silyl functionality.
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    • Styrene and n-butyl acrylate were also tested as olefin substrates, but neither showed any reactivity with the current catalyst system
    • Styrene and n-butyl acrylate were also tested as olefin substrates, but neither showed any reactivity with the current catalyst system.
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    • 3-induced rate enhancement could result from the higher reactivity of C-H activation with an electron-poor aryl, or from the higher reactivity of intramolecular addition to an electron-poor imine electrophile.
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    • Attempted substrates include acetophenone, benzophenone, Nphenyl benzophenone imine, N-tert-butyl benzaldimine, and benzophenone O-pentafluorobenzoyl oxime
    • Attempted substrates include acetophenone, benzophenone, Nphenyl benzophenone imine, N-tert-butyl benzaldimine, and benzophenone O-pentafluorobenzoyl oxime.
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    • This preparation proceeded with high chemical yields (<80%); the low yield of the isolated product reflected the solubility issue during crystallization
    • This preparation proceeded with high chemical yields (<80%); the low yield of the isolated product reflected the solubility issue during crystallization.
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    • See the Supporting Information for details
    • See the Supporting Information for details.
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    • GC analysis was carried out after the reaction was quenched with dry MeOH. The major product was the recovered benzophenone imine 1a.
    • GC analysis was carried out after the reaction was quenched with dry MeOH. The major product was the recovered benzophenone imine 1a.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.