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Volumn 50, Issue 17, 2011, Pages 3896-3899

Differentiating C-Br and C-Cl bond activation by using solvent polarity: Applications to orthogonal alkyl-alkyl negishi reactions

Author keywords

alkyl alkyl coupling; cross coupling; Negishi reaction; orthogonal reactions; solvent polarity

Indexed keywords

ALKYL-ALKYL COUPLING; CROSS-COUPLINGS; NEGISHI REACTIONS; ORTHOGONAL REACTION; SOLVENT POLARITY;

EID: 79954605817     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201100705     Document Type: Article
Times cited : (61)

References (46)
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    • Unactivated bromochloroalkanes were used previously in a two-pot orthogonal cross-coupling strategy, wherein the first cross-coupling was an aryl-alkyl or alkyl-alkyl Kumada-Tamao-Corriu reaction, and the subsequent reaction was a Sonogashira cross-coupling. The intrinsic reactivity of the C-Br bond relative to the C-Cl bond acted as the orthogonal "trigger". See.
    • Unactivated bromochloroalkanes were used previously in a two-pot orthogonal cross-coupling strategy, wherein the first cross-coupling was an aryl-alkyl or alkyl-alkyl Kumada-Tamao-Corriu reaction, and the subsequent reaction was a Sonogashira cross-coupling. The intrinsic reactivity of the C-Br bond relative to the C-Cl bond acted as the orthogonal "trigger". See:, O. Vechorkin, D. Barmaz, V. Proust, X. Hu, J. Am. Chem. Soc. 2009, 131, 12078-12079.
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    • PEPPSI is an acronym for pyridine-enhanced precatalyst preparation, stabilization, and initiation; IPr refers to the NHC ligand. [Pd-PEPPSI-IPr] is commerically available through Aldrich (Product # 669032). For reviews on [Pd-PEPPSI] catalysts, see
    • PEPPSI is an acronym for pyridine-enhanced precatalyst preparation, stabilization, and initiation; IPr refers to the NHC ligand. [Pd-PEPPSI-IPr] is commerically available through Aldrich (Product # 669032). For reviews on [Pd-PEPPSI] catalysts, see
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    • Inorganic salts, such as LiBr or LiCl, have been found to have a significant effect on the alkyl-alkyl Negishi reaction. For studies relating to this topic, see
    • Inorganic salts, such as LiBr or LiCl, have been found to have a significant effect on the alkyl-alkyl Negishi reaction. For studies relating to this topic, see:, G. T. Achonduh, N. Hadei, C. Valente, S. Avola, C. J. O'Brien, M. G. Organ, Chem. Commun. 2010, 46, 4109-4111.
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    • note
    • - to produce the corresponding alkyl bromide. This side reaction has the net effect of increasing the amount of 4, thus leading to a decrease in the observed or apparent selectivity. Although this side reaction has not been fully quantified, our observations indicate that it is minor in its contribution to 4.
  • 42
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    • note
    • The mass balance of 2 for each entry in Table 1 is attributed primarily to quenched (4-chlorobutyl)zinc bromide (volatility of 1-chlorobutane hinders quantification, b.p. 77-78°C), which is the product of disproportionation of nBuZnBr with 2. Trace (<5%) quantities of 1,8-dichlorooctane are observable in the GCMS chromatograms of each entry, suggesting that the intermediate (4-chlorobutyl)zinc bromide couples with 2 to some extent. Trace quantities of 1,4-dibromobutane (Finkelstein) and dodecane (coupling each site on 2) are observed in some entries. For the GCMS chromatograms of each entry, see Figure S2 in the Supporting Information.
  • 43
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    • note
    • Whereas 3.2 equiv of LiBr or LiCl is sufficient for the first cross-coupling, the second cross-coupling requires 6.4 equiv to achieve optimal conversions. For optimization studies, see Table S1 in the Supporting Information.
  • 44
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    • LiX is a byproduct in Rieke's method for organozinc formation. When Rieke organozincs are utilized, the total effective equivalents of LiX are reported. For the preparation of Rieke organozincs, see
    • LiX is a byproduct in Rieke's method for organozinc formation. When Rieke organozincs are utilized, the total effective equivalents of LiX are reported. For the preparation of Rieke organozincs, see


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.