Journal of the American Chemical Society
Page 4 of 6
Ph
Ni(PPh3)4 5 mol %
dcype 6 mol %
Ph
Supporting Information. Procedures, characterization of iso-
lated products, and mechanistic study. This material is available
O
Ph
(a)
Ph
+
1
Ph
water 10 mol %
diglyme, 110 oC, 24 h
CH3
Ph
3bg'
89% yield, ratio 1.8:1
Ni
(PhBO)3 (x 0.5)
2
3
P
3bg
standard condition
P
h3-benzyl complex
4
5
6
7
AUTHOR INFORMATION
Ph
CH3
Ph
O
Corresponding Author
(b)
+
Ph
(PhBO)3 (x 0.5)
Ph
Ph
CH3
standard
condition
3bh
3bh'
82% yield, ratio 1.9:1
8
9
ACKNOWLEDGMENT
We thank Singapore Ministry of Education Academic Research
Fund (MOE2013-T2-2-057, MOE2014-T1-001-021, MOE2015-T1-
001-166) for financial support.
P
Ph
Ph
P
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Ni
Ph
O
O
O
(c)
3bi
+
standard
condition
Ph
(PhBO)3 (x 1)
Ph
Ph
h3-benzyl complex
3bi'
85% yield, ratio 1:1
Ph
REFERENCES
P
O
P
Ni
(d)
3bj
standard
condition
+
Ph
h3-allyl complex
(1) Examples: (a) Nishimata, T.; Sato, Y.; Mori, M. J. Org. Chem. 2004, 69,
1837-1843. (b) White, L. V.; Schwartz, B. D.; Banwell, M. G.; Willis, A. C. J.
Org. Chem. 2011, 76, 6250-6257. (c) Singh, C.; Hassam, M.; Verma, V. P.;
Singh, A. S.; Naikade, N. K.; Puri, S. K.; Maulik, P. R.; Kant, R. J. Med.
Chem. 2012, 55, 10662-10673.
(2) Examples: (a) Chen, X.; Wehle, S.; Kuzmanovic, N.; Merget, B.;
Holzgrabe, U.; König, B.; Sotriffer, C. A.; Decker, M. ACS Chem. Neurosci.
2014, 5, 377-389. (b) Irie, M.; Fukaminato, T.; Matsuda, K.; Kobatake, S.
Chem. Rev. 2014, 114, 12174-12277. (c) Velema, W. A.; Szymanski, W.;
Feringa, B. L. J. Am. Chem. Soc. 2014, 136, 2178-2191. (d) Göstl, R.;
Hecht, S. Chem.-Eur. J. 2015, 21, 4422-4427. (e) Faulkner, A.; van
Leeuwen, T.; Feringa, B. L.; Wezenberg, S. J. J. Am. Chem. Soc. 2016, 138,
13597-13603.
(3) (a) Heck, R. F. Org. React. 1982, 27, 345–390. (b) Itami, K.; Nokami,
T.; Ishimura, Y.; Mitsudo, K.; Kamei, T.; Yoshida, J.-i. J. Am. Chem. Soc.
2001, 123, 11577-11585. (c) Jiao, J.; Nakajima, K.; Nishihara, Y. Org. Lett.
2013, 15, 3294-3297. (d) Tang, J.; Hackenberger, D.; Goossen, L. J.
Angew. Chem. Int. Ed. 2016, 55, 11296-11299.
(4) (a) Imamoto, T.; Takiyama, N.; Nakamura, K.; Hatajima, T.; Kamiya, Y.
J. Am. Chem. Soc. 1989, 111, 4392-4398. (b) Hilt, G.; Bolze, P.; Heitbaum,
M.; Hasse, K.; Harms, K.; Massa, W. Adv. Synth. Catal. 2007, 349, 2018-
2026. (c) Hatano, M.; Ishihara, K. Synthesis 2008, 1647-1675. (d)
Tallineau, J.; Bashiardes, G.; Coustard, J. M.; Lecornue, F. Synlett 2009,
2761-2764. (e) Butler, J. D.; Conrad, W. E.; Lodewyk, M. W.; Fettinger, J.
C.; Tantillo, D. J.; Kurth, M. J. Org. Lett. 2010, 12, 3410-3413.
(5) (a) Berthiol, F.; Doucet, H.; Santelli, M. Tetrahedron Lett. 2003, 44,
1221-1225. (b) Wu, X.; Lu, Y.; Hirao, H.; Zhou, J. Chem.-Eur. J. 2013, 19,
6014-6020. (c) Wu, X.; Zhou, J. Chem. Commun. 2013, 49, 4794-4796.
(6) (a) Qin, L.; Ren, X.; Lu, Y.; Li, Y.; Zhou, J. Angew. Chem. Int. Ed. 2012,
51, 5915-5919. (b) Qin, L.; Hirao, H.; Zhou, J. Chem. Commun. 2013, 49,
10236-10238. (c) Zou, Y.; Qin, L.; Ren, X.; Lu, Y.; Li, Y.; Zhou, J. Chem.-Eur.
J. 2013, 19, 3504 – 3511. (d) Zheng, C.; Stahl, S. S. Chem. Commun. 2015,
51, 12771-12774.
(7) Examples: (a) Littke, A. F.; Dai, C.; Fu, G. C. J. Am. Chem. Soc. 2000,
122, 4020-4028. (b) Scheiper, B.; Bonnekessel, M.; Krause, H.; Fürstner,
A. J. Org. Chem. 2004, 69, 3943-3949. (c) Hansen, A. L.; Ebran, J.-P.;
Gogsig, T. M.; Skrydstrup, T. Chem. Commun. 2006, 4137-4139. (d) Li, B.-
J.; Yu, D.-G.; Sun, C.-L.; Shi, Z.-J. Chem.-Eur. J. 2011, 17, 1728-1759.
(8) Examples: (a) Banwell, M. G.; Harvey, J. E.; Hockless, D. C. R.; Wu, A.
W. J. Org. Chem. 2000, 65, 4241-4250. (b) Examples: Thalén, L. K.; Zhao,
D.; Sortais, J.-B.; Paetzold, J.; Hoben, C.; Bäckvall, J.-E. Chem.-Eur. J. 2009,
15, 3403-3410.
(9) (a) Barluenga, J.; Moriel, P.; Valdés, C.; Aznar, F. Angew. Chem. Int.
Ed. 2007, 46, 5587-5590. (b) Barluenga, J.; Escribano, M.; Aznar, F.;
Valdés, C. Angew. Chem. Int. Ed. 2010, 49, 6856-6859. (c) Brachet, E.;
Hamze, A.; Peyrat, J.-F.; Brion, J.-D.; Alami, M. Org. Lett. 2010, 12, 4042-
4045. (d) Barluenga, J.; Valdés, C. Angew. Chem. Int. Ed. 2011, 50, 7486-
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(10) (a) Ojha, D. P.; Prabhu, K. R. J. Org. Chem. 2012, 77, 11027-11033.
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Ph
(PhBO)3 (x 1)
3bj'
83% yield, ratio 2.2:1
Figure 6. Arylation of two methyl ketones, 1,4-dione and -enone
Barluenga condition
Ph
Ph
NNHTs
Pd2(dba)3 (2 mol%)
XPhos (4 mol%)
(a)
+
PhBr
CO2Me
CO2Me
CO2Me
3ar CO2Me
CO2Me
CO2Me
LiOtBu (x 2.4)
dioxane, 110 oC, 15 h
3ar'
4a
Barluenga condition: 54% 3ar + 3ar' (1.2:1)
Nickel catalysis:
93% 3ar + 3ar' (1.8:1)
NNHTs
Br
NH2
(b)
NH2
+
Ph
Ph
Ph
4b
5a
3n
Barluenga condition:
6% 3n, 29% 5a
Barluenga, with K3PO4: 41% 3n, 1% 5a
Nickel catalysis:
PhBr
83% 3n, 0% 5a
Ph
N
HN
NNHTs
(c)
Ph
+
+
4c
3bj
3bj'
5b
Barluenga condition: 3% 3bj + 3bj', 85% 5b
Nickel catalysis:
83% 3bj + 3bj' (2.2:1)
NNHTs
Br
(d)
OMe
N
H
4d
N
OMe
H
3ac
Barluenga condition: 0% 3ac
Nickel catalysis:
64% 3ac
NNHTs
(e)
Ph
+
Ph
PhBr
N
N
N
3ab
5c
CO2Et
Ph
CO2Et 4e
Barluenga condition: 0% 3ab, 4% 5c
Nickel catalysis: 78% 3ab, 0% 5c
Figure 7. Barleunga arylation of hydrazones andcomparison with
nickel catalysis.
In summary, we report a general method to access aryl olefins
from ketones using arylboroxines. The neutral condition has a
distinct advantage by allowing direct generation of some arylole-
fins carrying acidic protons or sensitive groups.
ASSOCIATED CONTENT
(11) Examples: (a) Tobisu, M.; Xu, T.; Shimasaki, T.; Chatani, N. J. Am.
Chem. Soc. 2011, 133, 19505-19511. (b) Cornella, J.; Zarate, C.; Martin, R.
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