ACS Catalysis
Page 4 of 5
to furnish the product and V 18
I
CsOAc regenerates .
.
Finally, a transmetalation with
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1
2
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[Si]–H
CsI
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[Cu] OAc
[Si]–OAc
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CsOAc
[Cu]
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[Cu]
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H
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Me
Ph
V
Me
Ph
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4
Me
10
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44
45
46
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48
49
50
51
52
53
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55
56
57
58
59
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Me
I
[Cu]
Ar
[Cu]
III
Ph
IV
7
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Ar-I
Scheme 3. Proposed catalytic cycle
In conclusion, a Cu-catalyzed hydroarylation reaction has been
developed. Yields ranging from 32-99% are obtained with regioiso-
meric ratios of 7.2-44:1 as single diastereomers in all cases. A variety
of electronically and sterically differentiated alkynes and aryl iodides
are competent coupling partners, and the reaction is readily scalable.
Initial mechanistic studies show electronic bias of the alkyne is the
source of regioselectivity in the hydrocupration step and the oxida-
tive addition/reductive elimination sequence is likely a two-electron
process.
8 Manan, R. S.; Zhao, P. Nat. Commun. 2016, 7, 11506-11517.
9
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C.; Krause, N.; Lipshutz, B, H. Chem. Rev. 2008, 108, 2916-2927. (d) Fujihara,
T.; Semba, K.; Terao, J.; Tsuji, Y. Catal. Sci. Technol. 2014, 4, 1699-1709.
11 Daeuble, J. F.; McGettigan, C.; Stryker, J. M. Tetrahedron Lett. 1990, 31, 2397-
2400.
AUTHOR INFORMATION
Corresponding Author
*kamihull@illinois.edu
12 Fujihara, T.; Xu, T.; Semba, K.; Terao, J.; Tsuji, Y. Angew. Chem. Int. Ed. 2011
,
50, 523-527.
13
(a) Semba, K.; Fujihara, T.; Terao, J.; Tsuji, Y. Chem. Eur. J. 2012, 18, 4179-
4184. (b) Jang, W, J.; Lee, W. L.; Moon, J. H.; Lee, J. L.; Yun, J. Org. Lett. 2016
18, 1390-1393.
,
Notes
14 Shi, S.-L.; Buchwald, S. L. Nature Chem. 2015, 7, 38-44.
15 (a) Uehling, M. R.; Rucker, R. P.; Lalic, G. J. Am. Chem. Soc. 2014. 136,
8799-8803. (b) Suess, A. M.; Lalic, G. Synlett. 2016, 27, 1165-1174.
16 (a) Uehling, M. R.; Suess, A. M.; Lalic, G. J. Am. Chem. Soc. 2015, 137, 1424-
1427. (b) Malig, M..; Hazra, A.; Armstrong, M. K.; Lalic, G. J. Am. Chem. Soc.
2017, 139, 6969-6977.
The authors declare no competing financial interests.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website.
17 (a) Semba, K.; Ariyama, K.; Zheng, H.; Kameyama, R.; Sakaki, S.; Nakao, Y.
Angew. Chem. Int. Ed. 2016, 55, 6275-6279. (b) Friis, S. D.; Prinot, M. T.;
Experimental procedures and characterization data
(PDF)
Crystallographic data for 3d (CIF)
Buchwald, S. L. J. Am. Chem. Soc. 2016, 138, 8372-8375. (c) Friis, S. D.; Pirnot,
M. T.; Dupuis, L. N.; Buchwald, S. L. Angew. Chem. Int. Ed. 2017, 56, 7242-
7246.
18 (a) Shrestha, B.; Thapa, S.; Gurung, S. K.; Pike, R. A. S.; Giri, R.; J. Org.
Chem. 2016, 81, 787-802. (b) Basnet, P.; Thapa, S.; Dickie, D. A.; Giri, R.
Chem. Commun. 2016, 52, 11072-11075. (c) Thapa, S. T.; Basnet, P.; Giri, R. J.
Am. Chem. Soc. 2017, 139, 5700-5703.
ACKNOWLEDGMENT
The authors thank the University of Illinois and the NSF CAREER A-
ward (1555337) for their generous support.
19 (a) Zhou, Y.; You, W.; Smith, K. B.; Brown, M. K. Angew. Chem. Int. Ed.
2014, 53, 3475-3479. (b) You, W.; Brown, M. K. J. Am. Chem. Soc. 2015, 137,
14578-14581.
20
Bandar, J. S.; Pirnot, M. T.; Buchwald, S. L. J. Am. Chem. Soc. 2015, 137,
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