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Volumn 132, Issue 51, 2010, Pages 18078-18091

Alternative mechanistic explanation for ligand-dependent selectivities in copper-catalyzed N- and O-arylation reactions

Author keywords

[No Author keywords available]

Indexed keywords

AMINO ALCOHOLS; ARYLATION REACTIONS; ARYLATIONS; DIKETONES; IODINE ATOMS; IODOBENZENE; MEDIATED REACTIONS; N-ARYLATIONS; OXIDATIVE ADDITIONS; PHENANTHROLINES; POSITIVELY CHARGED; RATE-LIMITING STEPS; REDUCTIVE ELIMINATION; SINGLE ELECTRON TRANSFER; TRANSITION STATE;

EID: 78650628456     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja104264v     Document Type: Article
Times cited : (196)

References (173)
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    • For β -diketone type ligands in Cu-catalyzed cross coupling reactions, see
    • For β -diketone type ligands in Cu-catalyzed cross coupling reactions, see
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    • For diol type ligands in Cu-catalyzed C-X cross couplings, see
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    • Representative total syntheses involving Cu-catalyzed C-N cross couplings
    • Representative total syntheses involving Cu-catalyzed C-N cross couplings
  • 80
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    • Representative total syntheses involving Cu-catalyzed C-O cross couplings
    • Representative total syntheses involving Cu-catalyzed C-O cross couplings
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    • Ph.D. Dissertation, University of Massachusetts, Amherst, MA.
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    • For previous examples supporting the use of B3LYP to study Cu chemistry, see
    • For previous examples supporting the use of B3LYP to study Cu chemistry, see
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    • note
    • Considering that the B3LYP functional was reported to be problematic in treating some transition-metal systems, we also evaluated the effects of density functionals in this study. All the selected species shown in the following table were fully optimized with the same basis set as B3LYP calculations. Solvation effects were calculated with different functionals (the evaluation of different density functionals were also performed in the previous theoretical study of ref 15). The results show that for the oxidative addition/reductive elimination pathway, different DFT methods give a consistent picture on the observed selectivity. As shown in the table below, all the density functionals predict that L1-Int3a′ is more stable than L1-Int3c, and L2-TS1a is more stable than L2-TS4b. Therefore, the theoretical selectivity is not dependent on the density functionals.
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    • 78650624488 scopus 로고    scopus 로고
    • The β -diketone-mediated selective N -arylation of aminopentanol was also observed when the solvent was butyronitrile with ε = 20.7 (see ref 14).
    • The β -diketone-mediated selective N -arylation of aminopentanol was also observed when the solvent was butyronitrile with ε = 20.7 (see ref 14).
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    • I-catalyzed N -arylation of amides
    • I-catalyzed N -arylation of amides
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    • I-catalyzed arylation of nucleophiles using butadienylphosphine as ligand
    • I-catalyzed arylation of nucleophiles using butadienylphosphine as ligand
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    • I precatalyst in Cu-catalyzed O -arylation reactions, see
    • I precatalyst in Cu-catalyzed O -arylation reactions, see
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    • III catalytic cycle was explicitly suggested in recent experimental studies
    • III catalytic cycle was explicitly suggested in recent experimental studies
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    • III cycle through oxidative addition/reductive elimination
    • III cycle through oxidative addition/reductive elimination
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    • III was suggested to be formed during the coupling of aryl halides with amides/amines, see
    • III was suggested to be formed during the coupling of aryl halides with amides/amines, see
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    • III complexes have been characterized recently
    • III complexes have been characterized recently
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    • During the transformations of L1-Int3b → L1-Int3a' and L1-Int3b → L1-Int3c, the major contribution to the free energy comes from the entropy.
    • During the transformations of L1-Int3b → L1-Int3a' and L1-Int3b → L1-Int3c, the major contribution to the free energy comes from the entropy.
  • 168
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    • 3 is calculated to be highly endergonic, that is, +13.6 and +34.0 kcal/mol for the alcohol and amine groups, respectively.
    • 3 is calculated to be highly endergonic, that is, +13.6 and +34.0 kcal/mol for the alcohol and amine groups, respectively.
  • 169
    • 78650618781 scopus 로고    scopus 로고
    • - substitution/nucleophile coordination pathway together with direct reductive elimination on L1-Int5a / L1-Int5b are provided in Supporting Information.
    • - substitution/nucleophile coordination pathway together with direct reductive elimination on L1-Int5a / L1-Int5b are provided in Supporting Information.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.