Journal of the American Chemical Society
Page 4 of 5
mation has been demonstrated by late-stage functionalization of
1
2
3
active pharmaceutical reagents and by synthesis of key structures
of 11β-HSD1 inhibitors. The extension of this work to polymer
synthesis is currently in progress.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
4
5
6
7
8
9
a)
6x10-4M
2
This work was supported by Colorado State University, Universi-
ty of Colorado Boulder, and the Advanced Research Projects
Agency-Energy (DE-AR0000683). Research reported in this pub-
lication was supported by the National Institute of General Medi-
cal Sciences of the National Institutes of Health under Award
Number R35GM119702. We acknowledge the use of XSEDE
supercomputing resources (NSF ACI-1053575).
λmax = 306nm
1.5
1a
2a
1
1a+2a
1a+Cs2CO3
0.5
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
2a+Cs2CO3
1a+2a+Cs2CO3
0
300
350
400
REFERENCES
Wavelength (nm)
(1) (a) Feng, M.; Tang, B.; Liang, S.; Jiang, X. Curr. Top. Med. Chem.
2016, 16, 1200−1216. (b) Patani, G. A.; LaVoie, E. J. Chem. Rev. 1996,
96, 3147−3176. (c) Ilardi, E. A.; Vitaku, E.; Njardarson, J. T. J. Med.
Chem. 2014, 57, 2832−2842. (d) Boyd, D. A. Angew. Chem., Int. Ed. 2016,
55, 15486−15502. (e) Rahate, A. S.; Nemade, K. R.; Waghuley, S. A. Rev.
Chem. Eng. 2013, 29, 471−489.
b)
2
1.5
1
0.1M
1a
2a
1a+2a
(2) (a) Hartwig, J. F. Acc. Chem. Res. 2008, 41, 1534–1544. (b) Beletska-
ya, I. P.; Ananikov, V. P. Chem. Rev. 2011, 111, 1596–1636.
EDA
complex
1a+Cs2CO3
2a+Cs2CO3
1a+2a+Cs2CO3
0.5
0
(3) (a) Kwong, F. Y.; Buchwald, S. L. Org. Lett. 2002, 4, 3517–3520. (b)
Murata, M.; Buchwald, S. L. Tetrahedron 2004, 60, 7397–7403. (c) Fer-
nández-Rodríguez, M. A.; Shen, Q.; Hartwig, J. F. J. Am. Chem. Soc.
2006, 128, 2180–2181. (d) Alvaro, E.; Hartwig, J. F. J. Am. Chem. Soc.
2009, 131, 7858–7868. (e) Sayah, M.; Organ, M. G. Chem. Eur. J. 2011,
17, 11719–11722. (f) Gogoi, P.; Hazarika, S.; Sarma, M. J.; Sarma, K.;
Barman, P. Tetrahedron 2014, 70, 7484–7489.
(4) (a) Nicewicz, D. A.; MacMillan, D.W. C. Science 2008, 322, 77–80.
(b) Ischay, M. A.; Anzovino, M. E.; Du, J.; Yoon, T. P. J. Am. Chem. Soc.
2008, 130, 12886–12887. (c) Narayanam, J. M. R.; Tucker, J. W.; Ste-
phenson, C. R. J. J. Am. Chem. Soc. 2009, 131, 8756–8757.
400
450
500
550
600
Wavelength (nm)
c)
λcalc,1 = 282nm (f=0.137)
35% (πHOMO-πLUMO+4
32% (πHOMO-πLUMO+5
)
)
HOMO
LUMO
λcalc,2 = 383nm (f=0.036)
98% (πHOMO-πLUMO
)
̈
(5) Wang, X.; Cuny, G. D.; Noel, T. Angew. Chem., Int. Ed. 2013, 52,
7860–7864.
LUMO+4
LUMO+5
(6) (a) Oderinde, M. S.; Frenette, M.; Robbins, D. W.; Aquila, B.; Johan-
nes, J. W. J. Am. Chem. Soc. 2016, 138, 1760–1763. (b) Jouffroy, M.;
Kelly, C. B.; Molander, G. A. Org. Lett. 2016, 18, 876−879.
(7) Jiang, M.; Li, H.; Yang, H.; Fu, H. Angew. Chem., Int. Ed. 2017, 56,
874–879.
(8) (a) Bunnett, J. F.; Creary, X. J. Org. Chem. 1974, 39, 3173−3174. (b)
Uyeda, C.; Tan, Y.; Fu, G. C.; Peters, J. C. J. Am. Chem. Soc. 2013, 135,
9548–9552. (c) Johnson, M. W.; Hannoun, K. I.; Tan, Y.; Fu, G. C.; Pe-
ters, J. C. Chem. Sci. 2016, 7, 4091–4100.
(9) (a) Theriot, J. C.; Lim, C.-H.; Yang, H.; Ryan, M. D.; Musgrave, C.
B.; Miyake, G. M. Science 2016, 352, 1082−1086. (b) Pearson, R. M.;
Lim, C.-H.; McCarthy, B. G.; Musgrave, C. B.; Miyake, G. M. J. Am.
Chem. Soc. 2016, 138, 11399−11407. (c) Ya, D.; Pearson, R. M.; Lim, C.-
H.; Sartor, S. M.; Ryan, M. D.; Yang, H.; Damrauer, N. H.; Miyake, G. M.
Chem. Eur. J. 2017,23, 10962−10968. (d) Theriot, J. C.; McCarthy, B. G.;
Lim, C.-H.; Miyake, G. M. Macromol. Rapid Commun. 2017, 13,
1700040.
d)
Figure 1: UV-Vis absorption spectra of mixtures of 1a, 2a and
Cs2CO3 in DMSO (path length = 1cm) at concentrations of (a)
6x10-4 M and (b) 0.1 M for each species; (inset) a photograph
showing the formation of a yellow compound (proposed EDA
complex) when 1a, 2a, and Cs2CO3 were mixed together. (c)
Time-dependent DFT calculations to predict UV-Vis absorptions
of the EDA complex. (d) Proposed mechanism for visible-light
induced C-S cross-coupling.
(10) Rossi, R. A.; Pierini, A. B.; Peñéñory, A. B. Chem. Rev. 2003, 103,
71−168.
(11) See supporting information for further information.
(12) For reviews, see: (a) Rosokha, S. V.; Kochi, J. K. Acc. Chem. Res.
2008, 41, 641−653. (b) Lima, C. G. S.; Lima, T. M.; Duarte, M.; Jurberg,
I. D.; Paixao, M. W. ACS Catal. 2016, 6, 1389−1407.
̃
(13) Grushin, V.; Alper, H. Chem. Rev. 1994, 94, 1047–1062.
(14) Yan, X.; Wang, Z.; Sudom, A.; Cardozo, M.; DeGraffenreid, M.; Di,
Y.; Fan, P.; He, X.; Jaen, J. C.; Labelle, M.; Liu, J.; Ma, J.; McMinn, D.;
Miao, S.; Sun, D.; Tang, L.; Tu, H.; Ursu, S.; Walker, N.; Ye, Q.; Powers,
J. P. Bioorg. Med. Chem. Lett. 2010, 20, 7071−7075.
ASSOCIATED CONTENT
Supporting Information
Experimental procedures, mechanistic experiments, and
spectral data. This material is available free of charge via
(15) For examples of visible-light-induced EDA chemistry, see: (a) Arceo,
E.; Jurberg, I. D.; Alvarez-Fernandez, A.; Melchiorre, P. Nat. Chem. 2013,
́
́
5, 750−756. (b) Beatty, J. W.; Douglas, J. J.; Miller, R.; McAtee, R. C.;
Cole, K. P.; Stephenson, C. R. J. Chem. 2016, 1, 456−472 (c) (d) Sun, X.;
Wang, W.; Li, Y.; Ma, J.; Yu, S. Org. Lett. 2016, 18, 4638−4641. (d)
Deng, Y.; Wei, X.-J.; Wang, H.; Sun, Y.; Nöel, T.; Wang, X. Angew.
Chem., Int. Ed. 2017, 56, 832−836. (e) Candish, L.; Teders, M.; Glorius,
F. J. Am. Chem. Soc. 2017,139, 7440−7443.
AUTHOR INFORMATION
Corresponding Author
*garret.miyake@colostate.edu
ACS Paragon Plus Environment