Journal of the American Chemical Society
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(17) For other examples of Cu-catalyzed Negishi coupling, see: (a)
Malosh, C. F.; Ready, J. M. J. Am. Chem. Soc. 2004, 126, 10240; (b)
Thapa, S.; Vangala, A. S.; Giri, R. Synthesis 2016, 48, 504.
(18) Activated zinc (Zn*) was prepared by the Rieke method by
reducing ZnCl2 with potassium naphthalenide. See: (a) Rieke, R. D.
Science 1989, 246, 1260; (b) Zhu, L.; Wehmeyer, R. M.; Rieke, R. D. J.
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(19) For additional references for making alkylzinc reagents, see: (a)
Guijarro, A.; Rosenberg, D. M.; Rieke, R. D. J. Am. Chem. Soc. 1999,
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(20) Raising the temperature to 60 °C generally increases the
cyclization/cross-coupling by 5-10% with the corresponding decrease in
direct cross-coupling products.
(21) Reaction of 7-bromo-1-hexene-derived alkyl-ZnBr with 5-bromo-
2-iodopyrimidine did not generate any 6-membered cyclization/cross-
coupling product.
(22) No dehalogenation of products such as 17 was observed for all
entries in Tables 2-4 containing similar compounds.
(23) Reaction of 1-(cinnamyloxy)-2-iodobenzene-derived aryl-ZnBr
bearing an internal olefin with 5-bromo-2-iodopyrimidine did not generate
any cyclization/cross-coupling product.
2
007, 72, 3145; (g) Hu, N.; Li, K.; Wang, Z.; Tang, W. Angew. Chem. Int.
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(
m) Brenzovich, W. E.; Benitez, D.; Lackner, A. D.; Shunatona, H. P.;
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(10) For radical cyclization/cross-coupling of olefin-tethered alkyl
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(24) For a few examples of coupling with heteroaryl bromides and
synthesizing 3-benzyliodoline, see: ref. 12.
(25) The dr observed herein are similar for some compounds and
slightly different for others compared to those observed for a Ni-catalyzed
radical cyclization (see ref. 19b). The variation could arise from the use of
a ligand with the Ni-catalyst.
(26) Like 36, other olefin-tethered alkyl halides, except 5-hexenyl
bromide 1, also afforded cyclized alkylzinc reagents predominantly. 5-
Hexenyl bromide 1 furnished a 1:1 ratio of cyclized to uncyclized
alkylzinc reagent, which suggested that Cu-catalyst is also invloved in
cyclization of 5-hexenylzinc bromide. The result was further confirmed
with commercial 5-hexenylzinc bromide, which afforded the
cyclization/cross-coupling product 3 in 78% GC yield.
(11) Cong, H.; Fu, G. C. J. Am. Chem. Soc. 2014, 136, 3788.
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(
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3
(13) For examples of stable C(sp )-Cu complexes, see: (a) Janssen, M.
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(28) Prior results indicate that the migratory insertion of tethered
olefins into
a
ligand-bound aryl-Cu proceed with >20:1
diastereoselectivity. Under our conditions, the lower dr could also arise
due to the lack of an ancillary ligand. See ref. 12.
(29) Reaction of arylzinc reagent 54 in the presence of CuI and LiCl led
to partial decomposition of 54, which suggests that ArI is required during
the cyclization process.
2
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(
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