10.1002/chem.201802143
Chemistry - A European Journal
COMMUNICATION
1.
2.
3.
D. C. Blakemore, L. Castro, I. Churcher, D. C. Rees, A. W. Thomas, D.
M. Wilson, A. Wood, Nat. Chem. 2018, 10, 383–394.
[Ru(bpy)3]Cl2•6H2O
IBB
OH
Het
Ar
+
H–Het
2
C. A. Lipinski, F. Lombardo, B. W. Dominy, P. J. Feeney, Adv. Drug Del.
Rev. 1997, 23, 3–25.
Ar
O
CH2Cl2
40 °C, 24 h
7
Pharmaceuticals
Cl
A. Ziadi, N. Uchida, H. Kato, R. Hisamatsu, A. Sato, S. Hagihara, K.
Itami, K. U. Torii, Chem. Commun. 2017, 53, 9632–9635.
Meanwell, N. A. J. Med. Chem. 2011, 54, 2529–2591.
blue LED light
MeO
Me
4.
5.
6.
7.
SO2Ph
SO2Ph
N
N
E. F. V. Scriven, K. Turnbull Chem. Rev. 1988, 88, 298–368.
R. G. Johnson, R. K. Ingham, Chem. Rev. 1956, 56, 219–269.
M. F. Saraiva, M. R. C. Couri, M. L. Hyaric, M. V. de Almeida,
Tetrahedron 2009, 65, 3563–3572.
NH
Cl
SO2Ph
SO2Ph
SO2Ph
Ph
N
N
Me
F
SO2Ph
Cl
O
7a 59% (1.02 g, 47%)a
from Diclofenac
7b 44%
from Indomethacin
7c 73%
from Flurbiprofen
8.
9.
a) J. Xuan, Z.-G. Zhang, W.-J. Xiao, Angew. Chem., Int. Ed. 2015, 54,
15632–15641; b) H. Huang, K. Jia, Y. Chen, ACS Catal. 2016, 6, 4983–
4988. c) Y. Jin, H. Fu, Asian J. Org. Chem. 2017, 6, 368 – 385.
Important reviews and examples on non-photoredox-catalyzed
decarboxylation: a) Y. Wei, P. Hu, M. Zhang, W. Su, Chem. Rev. 2017,
117, 8864–8907; b) J. D. Weaver, A. Recio, A. J. Grenning, J. A. Tunge,
Chem. Rev. 2011, 111, 1846–1913; c) N. Rodriguez, L. J. Goossen,
Chem. Soc. Rev. 2011, 40, 5030–5048; d) P. J. Moon, S. Yin, R. J.
Lundgren, J. Am. Chem. Soc. 2016, 138, 13826–13829; e) N. R. Patel,
R. A. Flowers, II, J. Org. Chem. 2015, 80, 5834–5841; f) F. Yin, Z.
Wang, Z. Li, C. Li, J. Am. Chem. Soc. 2012, 134, 10401–10404; g) Z.
Wang, L. Zhu, F. Yin, Z. Su, Z. Li, C. Li, J. Am. Chem. Soc. 2012, 134,
4258–4263; h) G. J. P. Perry, J. M. Quibell, A. Panigrahi, I. Larrosa, J.
Am. Chem. Soc. 2017, 139, 11527–11536.
O
Me
O
Me
SO2Ph
SO2Ph
X
N
N
SO2Ph
SO2Ph
S
O
Me
Me
7d 54%
from Ibuprofen
7e 61%
from Zaltoprofen
7f (X = N(SO2Ph)2) 75%
7g (X = Cl) 82%b
from Isoxepac
Further derivatization: 7g + Nucleophile (Nu)c
O
O
O
O
S
N
S
O
CH3
10.
a) S. Ventre, F. R. Petronijevic, D. W. C. MacMillan, J. Am. Chem. Soc.
2015, 137, 5654–5657; b) L. Candish, E. A. Stamdlay, A. Gómez-
Suárez, S. Mukherjee, F. Glorius, Chem. Eur. J. 2016, 22, 9971–9974.
c) L. Candish, L. Pitzer, A. Gómez-Suárez, F. Glorius, Chem. Eur. J.
2016, 22, 4753–4756; d) F. L. Vaillant, M. D. Wodrich, J. Waser, Chem.
Sci. 2016, 8, 1790–1800.
NH2
O
O
8a 65%
(Nu = Duloxetine•HCl)
8b 48%
(Nu = L-Cysteine ethyl ester•HCl)
F3C
N
11.
12.
Representative examples of metallaphotoredox-catalyzed coupling with
organohalides: a) L. Fan, J. Jia, H. Hou, Q. Lefebvre, M. Rueping,
Chem. Eur. J. 2016, 22, 16437–16440; b) J. Luo, J. Zhang, ACS Catal.
2016, 6, 873–877; c) C. P. Johnston, R. T. Smith, S. Allmendinger, D.
W. C. MacMillan, Nature 2016, 536, 322–325.
N
O
CH3
O
O
O
O2S
O
O
N
O
a) S. B. Lang, K. C. Cartwright, R. S. Welter, T. M. Locascio, J. A.
Tunge, Eur. J. Org. Chem. 2016, 3331–3334; b) S. Inuki, K. Sato, Y.
Fujimoto, Tetrahedron Lett. 2015, 56, 5787–5790; c) Z. Fang, Y. Feng,
H. Dong, D. Li, T. Tang, Chem. Commun. 2016, 52, 11120–11123.
J. Liu, Q. Liu, H. Yi, C. Qin, R. Bai, X. Qi, Y. Lan, A. Lei, Angew. Chem.,
Int. Ed. 2014, 53, 502–506.
O
8c 43%
(Nu = Vitamin E)
8d 62%d
(Nu = Celecoxib)
13.
14.
15.
Figure 5. Transformation of pharmaceuticals. Optimized reaction conditions: 1
(2.0 equiv), 2 (0.20 mmol), [Ru(bpy)3]Cl2·6H2O (2.5 mol%), IBB (2.5 equiv),
a
K. Kiyokawa, T. Watanabe, L. Fra, T. Kojima, S. Minakata, J. Org.
Chem. 2017, 82, 11711–11720.
CH2Cl2 (4.0 mL) 40 °C, 24 h.
Diclofenac (2.0 equiv), 2a (4.0 mmol),
[Ru(bpy)3]Cl2·6H2O (2.5 mol%), IBB (2.5 equiv), CH2Cl2 (80 mL) 40 °C, 72 h. b
Isoxepac (2.0 equiv), Bu4N+Cl– (0.20 mmol), IBB (2.0 equiv), HN(SO2Ph)2 (25
mol%), [Ru(bpy)3]Cl2·6H2O (2.5 mol%), CH2Cl2 (4.0 mL) 40 °C, 24 h. c Nu (1.0
equiv), NaH (2.0 equiv), DMF (0.50 mL), 80 °C, 2 h. d Nu (0.50 equiv).
a) W. Zhao, R. P. Wurz, J. C. Peters, G. C. Fu, J. Am. Chem. Soc.
2017, 139, 12153–12156; b) R. Mao, A. Frey, J. Balon, X. Hu, Nat.
Catal. 2018, 1, 120–126; c) D. W. C. MacMillan, Y. Liang, X. Zhang,
2018, DOI 10.26434/chemrxiv.5877868.v1.
16.
17.
E. Ito, T. Fukushima, T. Kawakami, K. Murakami, K. Itami, Chem 2017,
2, 383–392.
Acknowledgments
Other important contributions on photoredox-catalyzed C–N bond
formation: a) Q. M. Kainz, C. D. Matier, A. Bartoszewicz, S. L. Zultanski,
J. C. Peters, G. C. Fu, Science 2016, 351, 681–684; b) N. A. Romero,
K. A. Margrey, N. E. Tay, D. A. Nicewicz, Science 2015, 349, 1326–
1330; c) L. Niu, H. Yi, S. Wang, T. Liu, J. Liu, A. Lei, Nat. Commun.
2017, 8, 14226; d) J. Davies, T. D. Svejstrup, D. F. Reina, N. S. Sheikh,
D. Leonori, J. Am. Chem. Soc. 2016, 138, 8092–8095.
This work was supported by the ERATO program from JST
(JPMJER1302 to K.I.), JSPS KAKENHI Grant Number
JP17H04868 (K.M.), and the Uehara Memorial Foundation
(K.M.). ITbM is supported by the World Premier International
Research Center Initiative (WPI), Japan. We thank Dr.
Shunsuke Oishi for fruitful discussions and Dr. Gregory J. P.
Perry for proofreading.
18.
19.
Q. Zhu, E. C. Gentry, R. R. Knowles, Angew. Chem., Int. Ed. 2016, 55,
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268–271; b) K. T. Tarantino, D. C. Miller, T. A. Callon, R. R. Knowles, J.
Am. Chem. Soc. 2015, 137, 6440–6443; c) J. C. K. Chu, T. Rovis,
Nature 2016, 539, 272–275.
Keywords: decarboxylation • photoredox catalyst • imidation •
ruthenium catalyst • arylacetic acid
20.
E. M. Sletten, C. R. Bertozzi, Angew. Chem., Int. Ed. 2009, 48, 6974–
6998.
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