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For examples of orthogonal cross-couplings in one-pot natural product syntheses, see
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aryl-O cross-couplings, see:, L. J. Gooßen, K. Gooßen, C. Stanciu, Angew. Chem. 2009, 121, 3621-3624
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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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For reviews on alkyl-alkyl cross-couplings, see
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35
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79954601226
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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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41
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79954614684
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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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79954603005
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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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79954616570
-
-
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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79954609079
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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
-
-
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