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Volumn 54, Issue 28, 2015, Pages 8259-8262

Design of New Ligands for the Palladium-Catalyzed Arylation of α-Branched Secondary Amines

Author keywords

amination; cross coupling; ligand design; palladium; synthetic methods

Indexed keywords

AMINATION; AMINES; AROMATIC COMPOUNDS; CATALYSIS; LIGANDS; PALLADIUM;

EID: 84930321922     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201502626     Document Type: Article
Times cited : (80)

References (66)
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    • For selected references containing examples of Pd-catalyzed C-N bond formation with α-branched secondary amines, see
    • For selected references containing examples of Pd-catalyzed C-N bond formation with α-branched secondary amines, see
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    • II salts (see Ref. [6c]). However, this is unlikely with the N-methyl 2-aminobiphenyl palladium methanesulfonate precatalysts used in this study because of their mechanism of activation, see Ref. [8a].
    • II salts (see Ref. [6c]). However, this is unlikely with the N-methyl 2-aminobiphenyl palladium methanesulfonate precatalysts used in this study because of their mechanism of activation, see Ref. [8a].
  • 43
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    • The presence of carbazole from the activation of the 2-amino biphenyl palladium methanesulfonate precatalysts inhibited the reaction. Therefore, the N-methyl 2-aminobiphenyl palladium methanesulfonate precatalysts were used instead.
    • The presence of carbazole from the activation of the 2-amino biphenyl palladium methanesulfonate precatalysts inhibited the reaction. Therefore, the N-methyl 2-aminobiphenyl palladium methanesulfonate precatalysts were used instead.
  • 48
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    • Experiments on a related substrate using a deuterated amine nucleophile have shown that the reduced arene product arises from a β-hydride elimination process.
    • Experiments on a related substrate using a deuterated amine nucleophile have shown that the reduced arene product arises from a β-hydride elimination process.
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    • II amido complex. See.
    • II amido complex. See:, J. F. Hartwig, Inorg. Chem. 2007, 46, 1936.
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    • Changing the substituents on the phosphorus from cyclohexyl to aryl groups can also reduce the size of the ligand, which could potentially make the catalyst more accommodating to larger amine nucleophiles.
    • Changing the substituents on the phosphorus from cyclohexyl to aryl groups can also reduce the size of the ligand, which could potentially make the catalyst more accommodating to larger amine nucleophiles.
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    • For examples of the effect of incorporating methoxy groups on the ligand biaryl structure in Pd-catalyzed carbon-heteroatom bond-forming reactions, see Refs. [9b,13a], and
    • For examples of the effect of incorporating methoxy groups on the ligand biaryl structure in Pd-catalyzed carbon-heteroatom bond-forming reactions, see Refs. [9b,13a], and:, X. Wu, B. P. Fors, S. L. Buchwald, Angew. Chem. Int. Ed. 2011, 50, 9943
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    • In this case, the difference in performance between ligands L6 and L7 was not significant. However, L7 performed considerably better than L6 in the reaction with other substrates, particularly aryl chlorides, see the Supporting Information.
    • In this case, the difference in performance between ligands L6 and L7 was not significant. However, L7 performed considerably better than L6 in the reaction with other substrates, particularly aryl chlorides, see the Supporting Information.
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    • The length of the C-F bond is more similar to the length of the C-O bond than to that of the C-H bond, making the steric effects of an ortho-fluoro substituent slightly more significant than those of an ortho-hydrogen substituent. See.
    • The length of the C-F bond is more similar to the length of the C-O bond than to that of the C-H bond, making the steric effects of an ortho-fluoro substituent slightly more significant than those of an ortho-hydrogen substituent. See:, K. Müller, C. Faeh, F. Diederich, Science 2007, 317, 1881.
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    • The amounts of the corresponding reduced arene and ArOtBu by-products that were observed have been indicated in the table footnotes. In most cases, these by-products could be readily separated from the desired aryl amine product. Only in the case of 2 c was the separation difficult and the isolated material contained less than 5 % of the corresponding ArOtBu.
    • The amounts of the corresponding reduced arene and ArOtBu by-products that were observed have been indicated in the table footnotes. In most cases, these by-products could be readily separated from the desired aryl amine product. Only in the case of 2 c was the separation difficult and the isolated material contained less than 5 % of the corresponding ArOtBu.
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    • The cross-coupling of diisopropylamine with 4-bromoanisole was reported by Herrmann to provide the aryl amine product in 78 % yield. In our hands, the products under these conditions resulted from the arylation of the corresponding N-isopropylpropan-2-imine see:, and the Supporting Information.
    • The cross-coupling of diisopropylamine with 4-bromoanisole was reported by Herrmann to provide the aryl amine product in 78 % yield. In our hands, the products under these conditions resulted from the arylation of the corresponding N-isopropylpropan-2-imine see:, W. A. Herrmann, V. P. W. Böhm, C.-P. Reisinger, J. Organomet. Chem. 1999, 576, 23 and the Supporting Information.
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    • A control experiment produced none of the arylated diisopropylamine or the corresponding ArOtBu, see the Supporting Information.
    • A control experiment produced none of the arylated diisopropylamine or the corresponding ArOtBu, see the Supporting Information.
  • 63
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    • An excess of amine relative to NaOtBu led to the incomplete conversion of the aryl electrophile. As such, the same amine-to-base ratio was maintained for all reactions, see the Supporting Information.
    • An excess of amine relative to NaOtBu led to the incomplete conversion of the aryl electrophile. As such, the same amine-to-base ratio was maintained for all reactions, see the Supporting Information.
  • 64
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    • Control experiments for substrates 3 a, 3 b, and 3 c showed no formation of the product or the corresponding ArOtBu, see the Supporting Information.
    • Control experiments for substrates 3 a, 3 b, and 3 c showed no formation of the product or the corresponding ArOtBu, see the Supporting Information.
  • 65
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    • When P7 was used, the yields of 3 a, 3 b and 3 c were 5 %, 60 %, and 70 % respectively, see the Supporting Information.
    • When P7 was used, the yields of 3 a, 3 b and 3 c were 5 %, 60 %, and 70 % respectively, see the Supporting Information.
  • 66
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    • See the Supporting Information.
    • See the Supporting Information.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.