ACS Catalysis
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For the coupling of acid chlorides with alkyl Grignard
The role of the N-substituents in amide C–N bond cleav-
reagents, see: Scheiper, B.; Bonnekessel, M.; Krause, H.;
age reactions is currently under investigation and will be
described elsewhere in due course.
Fürstner, A. J. Org. Chem. 2004, 69, 3943–3949.
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(
a) Zhang, Y.; Rovis, T. J. Am. Chem. Soc. 2004, 126,
N-Alkyl,Ts amides can be readily prepared by sulfona-
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5964–15965. (b) Cherney, A. H.; Reisman, S. E. Tetrahe-
mide coupling of the corresponding carboxylic acid or acid
halide (see the SI). For a discussion of the robustness of
sulfonamides and their stability, see: Searles, S.; Nukina, S.
Chem. Rev. 1959, 59, 1077–1103.
dron 2014, 70, 3259–3265. (c) Harada, T.; Kotani, Y.; Kat-
suhira, T.; Oku, A. Tetrahedron Lett. 1991, 32, 1573–1576.
0
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(
d) Negishi, E.-i.; Bagheri, V.; Chatterjee, S.; Luo, F.-T.;
Miller, J. A.; Stoll, A. T. Tetrahedron Lett. 1983, 24, 5181–
184. (e) Iwai, T.; Nakai, T.; Mihara, M.; Ito, T.; Mizuno,
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Substrates derived from aliphatic carboxylic acids do not
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couple under the reported reaction conditions; studies to
overcome this limitation are currently underway.
T.; Ohno, T. Synlett 2009, 1091–1094. (f) Grey, R. A. J.
Org. Chem. 1984, 49, 2288–2289. (g) Sato, T.; Naruse, K.;
Enokiya, M.; Fujisawa, T. Chem. Lett. 1981, 10, 1135–
1138.
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Lower yields of 12 were obtained using the correspond-
ing N-Me,Ts benzamide substrate. Generally, amides de-
rived from electron-poor arenes were found to couple in
higher yields when the N-Bn,Boc derivatives were em-
ployed.
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(a) Wang, D.; Zhang, Z. Org. Lett. 2003, 5, 4645–4648.
(b) Cook, M. J.; Rovis, T. Synthesis 2009, 335–338. (c)
Bercot, E. A.; Rovis, T. J. Am. Chem. Soc. 2002, 124, 174–
175. (d) Bercot, E. A.; Rovis, T. J. Am. Chem. Soc. 2005,
127, 247–254. (e) Johnson, J. B.; Cook, M. J.; Rovis, T.
Tetrahedron 2009, 65, 3202–3210. (f) Rogers, R. L.;
Moore, J. L.; Rovis, T. Angew. Chem. Int. Ed. 2007, 46,
9301–9304. (g) Bercot, E. A.; Rovis, T. J. Am. Chem. Soc.
2004, 126, 10248–10249. (h) Johnson, J. B.; Yu, R. T.;
Fink, P.; Bercot, E. A.; Rovis, T. Org. Lett. 2006, 8, 4307–
4310. (i) Johnson, J. B.; Bercot, E. A.; Rowley, J. M.;
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2718–2725. (j) Cook, M. J.; Rovis, T. J. Am. Chem. Soc.
2007, 129, 9302–9303.
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The organozinc bromide or iodide was used in accord
with literature precedent for the formation of each or-
ganozinc species. Generally, alkyl bromides and iodides are
known to undergo organozinc formation more readily than
alkyl chlorides; see ref. 9b.
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Although primary and secondary organozinc species
were well tolerated in the coupling, it was found that cou-
plings with tertiary organozinc halides and organozinc rea-
gents bearing heterocycles, acetals, and esters gave only
trace amounts of product.
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Han, C.; Buchwald, S. L. J. Am. Chem. Soc. 2009, 131,
7532–7533.
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(a) Tokuyama, H.; Yokoshima, S.; Yamashita, T.; Fuku-
For the Ni-catalyzed activation of methyl esters, see: Hie,
yama, T. Tetrahedron Lett. 1998, 39, 3189–3192. (b) Mori,
Y.; Seki, M. Tetrahedron Lett. 2004, 45, 7343–7345. (c)
Shimizu, T.; Seki, M. Tetrahedron Lett. 2002, 43, 1039–
L.; Fine Nathel, N. F.; Hong, X.; Yang, Y.-F.; Houk, K. N.;
Garg, N. K. Angew. Chem. Int. Ed. 2016, 55, 2810–2814.
See ref. 10 for alternative examples of ester activation us-
ing nickel catalysis.
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042. (d) Miyazaki, T.; Han-ya, Y.; Tokuyama, H.; Fuku-
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yama, T. Synlett 2004, 477–480. (e) Shimizu, T.; Seki, M.
Tetrahedron Lett. 2001, 42, 429–432. (f) Mori, Y.; Seki, M.
Adv. Synth. Catal. 2007, 349, 2027–2038.
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0120202834, August 9 , 2012.
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