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Chemical Science
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ARTICLE
Journal Name
12 (a) S. C. Blackstock, J. P. Lorand, J. K. Kochi, J. Org. Chem.,
1987, 52, 1451-1460; (b) Y. Cheng, X. Yuan, J. Ma, S. Yu, Chem.
Eur. J., 2015, 21, 8355-8359.
13 (a) T. A. Rokob, A. Hamza, A. Stirling, T. Soós, I. Pápai, Angew.
Chem. Int. Ed., 2008, 47, 2435-2438; (b) T. A. Rokob, A. Hamza,
A. Stirling, I. Pápai, J. Am. Chem. Soc., 2009, 131, 2029-2036;
(c) S. Grimme, H. Kruse, L. Goerigk, G. Erker, Angew. Chem.
Int. Ed., 2010, 49, 1402-1405; (d) M. Pu, T. Privalov, J. Chem.
DOI: 10.1039/D0SC01159B
J. Qin, X. Shen, R. Riedel, K. Harms, E. Meggers, Angew. Chem.
Int. Ed., 2016, 55, 685-688; (n) E. Fava, A. Millet, M. Nakajima,
S. Loescher, M. Rueping, Angew. Chem. Int. Ed., 2016, 55,
6776-6779; (o) L. Li, T. Xiao, H. Chen, L. Zhou, Chem. Eur. J.,
2017, 23, 2249-2254; (p) C.-W. Hsu, H. Sundén, Org. Lett.,
2018, 20, 2051-2054.
Phys., 2013, 138, 154305; (e) L. Rocchigiani, G. Ciancaleoni, C. 18 The generation of paramagnetic species in the solution of
Zuccaccia, A. Macchioni, J. Am. Chem. Soc., 2014, 136, 112-
115.
14 For seminal contributions to the exploitation of EDA-complex
B(C6F5)3 and N,N-dimethylaniline was described in W. E. Piers,
Adv. Organomet. Chem., 2005, 52, 1-76; however, the precise
analysis of the paramagnetic species has not been achieved.
formation in controlling catalytic bond formations, see: (a) E. 19 S. V. Rosokha, J. K. Kochi, Acc. Chem. Res., 2008, 41, 641-653.
Arceo, I. D. Jurberg, A. Álvarez-Fernández, P. Melchiorre, Nat. 20 T. Dahl, Acta Cryst. C, 1985, 41, 931-933.
Chem., 2013, 5, 750-756; (b) A. Bahamonde, P. Melchiorre, J. 21 Compound 4b was obtained in 57% yield with 10 equivalents
Am. Chem. Soc., 2016, 138, 8019-8030; (c) Z.-Y. Cao, T. Ghosh,
of 3a when THF was used as solvent.
P. Melchiorre, Nat. Commun., 2018, 9, 3274. For recent 22 (a) P. Kohls, D. Jadhav, G. Pandey, O. Reiser, Org. Lett., 2012,
examples of catalysis via EDA-complex formation, see: (d) R.
P. Shirk, S. S. V. Ramasastry, Org. Lett., 2017, 19, 5482-5485;
(e) I. Bosque, T. Bach, ACS Catal., 2019, 9, 9103-9109.
14, 672-675; (b) L. Ruiz Espelt, E. M. Wiensch, T. P. Yoon, J.
Org. Chem., 2013, 78, 4107-4114; (c) J. Xuan, T.-T. Zeng, Z.-J.
Feng, Q.-H. Deng, J.-R. Chen, L.-Q. Lu, W.-J. Xiao, H. Alper,
Angew. Chem. Int. Ed., 2015, 54, 1625-1628; (d) S.-X. Lin, G.-J.
Sun, Q. Kang, Chem. Commun., 2017, 53, 7665-7668; (e) J.
Zheng, B. Breit, Angew. Chem. Int. Ed., 2019, 58, 3392-3397.
15 (a) U. C. Yoon, J. U. Kim, E. Hasegawa, P. S. Mariano, J. Am.
Chem. Soc., 1987, 109, 4421-4423; (b) E. Hasegawa, W. Xu, P.
S. Mariano, U. C. Yoon, J. U. Kim, J. Am. Chem. Soc., 1988, 110,
8099-8111; (c) U. C. Yoon, P. S. Mariano, Acc. Chem. Res., 23 Performing the reaction with the light irradiation at fixed
1992, 25, 233-240; (d) D. W. Cho, U. C. Yoon, P. S. Mariano,
Acc. Chem. Res., 2011, 44, 204-215; (e) Y. Miyake, Y. Ashida,
K. Nakajima, Y. Nishibayashi, Chem. Commun., 2012, 48, 6966-
intervals under otherwise identical conditions revealed that
the bond formation proceeded only when irradiated (Fig.
S14).
6968; (f) Y. Miyake, Y. Ashida, K. Nakajima, Y. Nishibayashi, 24 We tried to determine the quantum yield of the reaction
Chem. Eur. J., 2014, 20, 6120-6125; (g) K. Nakajima, M.
Kitagawa, Y. Ashida, Y. Miyake, Y. Nishibayashi, Chem.
Commun., 2014, 50, 8900-8903; (h) D. Lenhart, T. Bach,
Beilstein J. Org. Chem., 2014, 10, 890-896; (i) L. Ruiz Espelt, I.
S. McPherson, E. M. Wiensch, T. P. Yoon, J. Am. Chem. Soc.,
reported in entry 1, Table 2 by the standard ferrioxalate
actinometry according to the literature procedure.25
However, the reaction did not proceed within the range of the
photon flux density that could be determined by the method,
indicating that the quantum yield was at least lower than 1.0.
2015, 137, 2452-2455; (j) K. Nakajima, Y. Ashida, S. Nojima, Y. 25 (a) C. G. Hatchard, C. A. Parker, Proc. R. Soc. London, 1956,
Nishibayashi, Chem. Lett., 2015, 44, 545-547; (k) C. Wang, Y.
Zheng, H. Huo, P. Röse, L. Zhang, K. Harms, G. Hilt, E. Meggers,
Chem. Eur. J., 2015, 21, 7355-7359; (l) D. Lenhart, A. Bauer, A.
235, 518-536; (b) M. A. Cismesia, T. P. Yoon, Chem. Sci., 2015,
6, 5426-5434; (c) C. B. Tripathi, T. Ohtani, M. T. Corbett, T. Ooi,
Chem. Sci., 2017, 8, 5622-5627.
Pöthig, T. Bach, Chem. Eur. J., 2016, 22, 6519-6523; (m) S.-Y. 26 (a) R. Mosca, M. Fagnoni, M. Mella, A. Albini, Tetrahedron,
Hsieh, J. W. Bode, Org. Lett., 2016, 18, 2098-2101; (n) T. Kizu,
D. Uraguchi, T. Ooi, J. Org. Chem., 2016, 81, 6953-6958; (o) W.
2001, 57, 10319-10328; (b) N. Hoffmann, S. Bertrand, S.
Marinković, J. Pesch, Pure Appl. Chem., 2006, 78, 2227-2246.
Ding, L.-Q. Lu, J. Liu, D. Liu, H.-T. Song, W.-J. Xiao, J. Org. 27 We conducted crossover experiments with 1b and excess
Chem., 2016, 81, 7237-7243; (p) Y. Zhao, J.-R. Chen, W.-J. Xiao,
Org. Lett., 2016, 18, 6304-6307; (q) C. Remeur, C. B. Kelly, N.
R. Patel, G. A. Molander, ACS Catal., 2017, 7, 6065-6069; (r) X.
Shen, Y. Li, Z. Wen, S. Cao, X. Hou, L. Gong, Chem. Sci., 2018,
9, 4562-4568; (s) Y. Cai, Y. Tang, L. Fan, Q. Lefebvre, H. Hou,
M. Rueping, ACS Catal., 2018, 8, 9471-9476; (t) A. Casado-
Sánchez, P. Domingo-Legarda, S. Cabrera, J. Alemán, Chem.
Commun., 2019, 55, 11303-11306; (u) M. Grübel, C. Jandl, T.
Bach, Synlett, 2019, 30, 1825-1829.
amount of 2 or 5a using 3a as an acceptor and B(C6F5)3 as a
catalyst (10 mol%) under dark conditions (see Scheme S2 for
details). In both cases, the formation of crossover product 4a
or 6a was not detected, and 4b was obtained as a sole
product. These results suggest that the intervention of the
radical-chain process is marginal.
16 (a) B. E. Cooper, W. J. Owen, J. Organomet. Chem., 1971, 29,
33-40; (b) H. Bock, W. Kaim, Acc. Chem. Res., 1982, 15, 9-17;
(c) J. Yoshida, T. Maekawa, T. Murata, S. Matsunaga, S. Isoe, J.
Am. Chem. Soc., 1990, 112, 1962-1970.
17 (a) A. McNally, C. K. Prier, D. W. C. MacMillan, Science, 2011,
334, 1114-1117; (b) Y. Miyake, K. Nakajima, Y. Nishibayashi, J.
Am. Chem. Soc., 2012, 134, 3338-3341; (c) H. Zhou, P. Lu, X.
Gu, P. Li, Org. Lett., 2013, 15, 5646-5649; (d) C. Zhang, C. Liu,
Y. Shao, X. Bao, X. Wan, Chem. Eur. J., 2013, 19, 17917-17925;
(e) C. K. Prier, D. W. C. MacMillan, Chem. Sci., 2014, 5, 4173-
4178; (f) A. Noble, D. W. C. MacMillan, J. Am. Chem. Soc.,
2014, 136, 11602-11605; (g) X. Dai, D. Cheng, B. Guan, W.
Mao, X. Xu, X. Li, J. Org. Chem., 2014, 79, 7212-7219; (h) X.
Dai, R. Mao, B. Guan, X. Xu, X. Li, RSC Adv., 2015, 5, 55290-
55294; (i) D. Uraguchi, N. Kinoshita, T. Kizu, T. Ooi, J. Am.
Chem. Soc., 2015, 137, 13768-13771; (j) K. Nakajima, Y.
Miyake, Y. Nishibayashi, Acc. Chem. Res., 2016, 49, 1946-
1956; (k) H. B. Hepburn, P. Melchiorre, Chem. Commun., 2016,
6 | J. Name., 2012, 00, 1-3
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