Journal of the American Chemical Society
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1 (a) Lu, R.ꢀJ.; Tucker, J. A.; Pickens, J.; Ma, Y.ꢀA.; Zinevitch, T.; Kirichenko, O.; Konoplev, V.; Kuznetsova, S.; Sviridov, S.; Brahmachary, E.; Khasanov, A.; Mikel, C.; Yang, Y.; Liu, C; Wang, J.;
Freel, S.; Fisher, S.; Sullivan, A.; Zhou, J.; StanfieldꢀOakley, S.; Baker, B.; Sailstad, J.; Greenberg, M.; Bolognesi, D.; Bray, B.; Koszalka, B.; Jeffs, P.; Jeffries, C.; Chucholowski, A.; Sexton, C. J. Med.
Chem. 2009, 52, 4481. (b) Senthil Kumar, N.; Arul Clement, J.; Mohanakrishnan, A. K. Tetrahedron 2009, 65, 822. (c) Bridges, T. M.; Kennedy, J. P.; Hopkins, C. R.; Conn, P. J.; Lindsley, C. W. Bioorg.
Med. Chem. Lett. 2010, 20, 5617. (d) Dua, R.; Shrivastava, S.; Sonwane, S. K.; Srivastava, S. K. Advan. Biol. Res. 2011, 5, 120. (e) Li, H. R.; Sun, S. Y.; Salim, T.; Bomma, S.; Grimsdale, A. C.; Lam, Y. M. J.
Polym. Sci., Part A: Polym. Chem. 2012, 50, 250. (f) Segawa, Y.; Maekawa, T.; Itami, K. Angew. Chem. Int. Ed. 2015, 54, 66.
2 For reviews, see: (a) Alberico, D.; Scott, M. E.; Lautens, M. Chem. Rev. 2007, 107, 174. (b) Seregin, I. V.; Gevorgyan, V. Chem. Soc. Rev. 2007, 36, 1173. (c) Ackermann, L.; Vicente, R.; Kapdi, A. R.
Angew. Chem. Int. Ed. 2009, 48, 9792. (d) Chen, X.; Engle, K. M.; Wang, D.ꢀH.; Yu, J.ꢀQ. Angew. Chem. Int. Ed. 2009, 48, 5094; (e) Bellina, F.; Rossi, R. Tetrahedron, 2009, 65, 10269. (f) Roger, J.; Gottuꢀ
mukkala, A. L.; Doucet, H. ChemCatChem. 2010, 2, 20. (g) Liu, W.; Cao, H.; Lei, A. Angew. Chem. Int. Ed. 2010, 49, 2004. (h) Liu, W.; Cao, H.; Xin, J.; Jin, L. Lei, A. Chem. Eur. J. 2011, 17, 3588. (i)
Lebrasseur, N.; Larrosa, I. In Advances in Heterocyclic Chemistry; Katritzky, A. R., Ed.; Elsevier: USA, 2012; pp. 309. (j) Rossi, R.; Bellina, F.; Lessi, M.; Manzini, C. Adv. Synth. Catal. 2014, 356, 17. (k)
Bonin, H.; Sauthier, M.; Felpin, F.ꢀX. Adv. Synth. Catal. 2014, 356, 645. (l) Djakovitch, L.; Felpin, F.ꢀX. ChemCatChem 2014, 6, 2175. (m) Sandtrov, A. H. Adv. Synth. Catal. 2015, 357, 2403.
3 (a) JuliaꢀHernandez, F.; Simonetti, M.; Larrosa, I. Angew. Chem. Int. Ed. 2013, 52, 11458. (b) Yang, J. Org. Biomol. Chem. 2015, 13, 1930.
4 WencelꢀDelord, J.; Dröge, T.; Liu, F.; Glorius, F. Chem. Soc. Rev. 2011, 40, 4740.
5 (a) Horton, D. A.; Bourne, G. T.; Smythe, M. L. Chem. Rev. 2003, 103, 893. (b) Murphy, A. R.; Frechet, J. M. J. Chem. Rev. 2007, 107, 1066. (c) Liu, Y.; Liu, Y.; Zhan, X. Macromol. Chem. Phys. 2011,
212, 428. (d) Wang, C.; Dong, H.; Hu, W.; Liu, Y.; Zhu, D. Chem. Rev. 2012, 112, 2208.
6 For selected examples of Cꢀ2 arylation of benzo[b]thiophene see: (a) Chabert, J. F. D.; Joucla, L.; David, E.; Lemaire, M. Tetrahedron 2004, 60, 3221. (b) Nandurkar, N. S.; Bhanushali, M. J.; Bhor, M.
D.; Bhanage, B. M. Tetrahedron Lett. 2008, 49, 1045. (c) Liégault, B.; Lapointe, D.; Caron, L.; Vlassova, A.; Fagnou, K. J. Org. Chem., 2009, 74, 1826. (d) Masuda, N.; Tanba, S.; Sugie, A.; Monguchi, D.;
Koumura, N.; Hara, K.; Mori, A. Org. Lett. 2009, 11, 2297. (e) René, O.; Fagnou, K. Adv. Synth. Catal. 2010, 352, 2116. (f) Tamba, S.; Okubo, Y.; Tanaka, S.; Monguchi, D.; Mori, A. J. Org. Chem., 2010,
75, 6998. (g) Baghbanzadeh, M.; Pilger, C.; Kappe, C. O. J. Org. Chem. 2011, 76, 8138. (h) Truong, T.; Daugulis, O. J. Am. Chem. Soc. 2011, 133, 4243. (i) Tanaka, S.; Tanaka, D.; Sugie, A.; Mori, A.
Tetrahedron Lett. 2012, 53, 1173. (l) Gosh, D.; Lee, H. M. Org. Lett. 2012, 14, 5534. (m) Martin, A. R.; Chartoire, A.; Slawin, A. M. Z.; Nolan, S. P. Beilstein J. Org. Chem. 2012, 8, 1637. (n) Zhao, L.;
Bruneau, C; Doucet, H. Tetrahedron 2013, 69, 7082. (o) DaoꢀHuy, T.; Haider, M.; Glatz, F.; Schnurch, M.; Mihovilovic, M. D. Eur. J. Org. Chem. 2014, 8119.
7 (a) Ueda, K.; Yanagisawa, S.; Yamaguchi, J.; Itami, K. Angew. Chem. Int. Ed. 2010, 49, 8946. (b) Kirchberg, S.; Tani, S.; Ueda, K.; Yamaguchi, J.; Studer, A.; Itami, K. Angew. Int. Ed. 2011, 50, 2387.
(c) Funaki, K.; Sato, T.; Oi, S. Org. Lett. 2012, 14, 6186. (d) Tang, D.ꢀT. D.; Collins, K. D.; Glorius, F. J. Am. Chem. Soc. 2013, 135, 7450. (e) Yuan, K.; Doucet, H. Chem. Sci. 2014, 5, 392. (f) Tang, D.ꢀT.
D.; Collins, K. D.; Ernst, J. B.; Glorius, F. Angew. Chem. Int. Ed. 2014, 53, 1809. ( (h) Maki, Y.; Goto, T.; Tsukada, N. ChemCatChem DOI: 10.1002/cctc.201501132
8 For examples of Cꢀ3 arylation using directing groups, see: (a) Schnapperelle, I.; Breitenlechner, S.; Bach, T. Org. Lett. 2011, 13, 3640. (b) Larbi, K. S.; Fu, H. Y.; Laidaoui, N.; Beydoun, K.; Miloudi, A.;
Abed, D. E.; Djabbar, S.; Doucet, H. ChemCatChem 2012, 4, 815.
9 (a) Lebrasseur, N.; Larrosa, I. J. Am. Chem. Soc. 2008, 130, 2926. (b) Islam, S.; Larrosa, I. Chem. Eur. J. 2013, 19, 15093.
10 Bégue, J.ꢀP.; BonnetꢀDelpon, D.; Crousse, B. Synlett, 2004, 1, 18.
11 Attempts at replacing Ag(I) salts with Me4Nꢀsalts were unsuccessful. See: Arroniz, C.; Denis, J. G.; Ironmonger, A.; Rassias, G.; Larrosa, I. Chem. Sci. 2014, 5, 3509.
12 In line with this observation, aryl chlorides and bromides were unreactive under reaction conditions. Aryl triflates were also found to be unreactive.
13 (a) Spicer, C. D.; Davis, B. G. Chem. Commun. 2011, 47, 1698. (b) Gao, Z.; Gouverneur, V.; Davis, B. G. J. Am. Chem. Soc. 2013, 135, 13612. (c) Dumas, A.; Spicer, C. D.; Gao, Z.; Takenhana, T.;
Lin, Y. A.; Yasukohchi, T.; Davis, B. G. Angew. Chem. Int. Ed. 2013, 52, 3916. (d) Spicer, C. D.; Davis, B. G. Nat. Commun. 2014, 5, 4740. (e) Dumas, A.; Lercher, L.; Spicer, C. D.; Davis, B. G. Chem. Sci.
2015, 6, 50.
14 For selected example of functionalization of aminoacids see: (a) Chalker, J. M.; Wood, C. S. C.; Davis, B. G. J. Am. Chem. Soc. 2009, 131, 16346. (b) RuizꢀRodríguez, J.; Albericio, F.; Lavilla, R.
Chem. Eur. J. 2010, 16, 1124. (c) Preciado, S.; MendiveꢀTapia, L.; Albericio, F.; Lavilla, R. J. Org. Chem. 2013, 78, 8129. (d) Gong, W.; Zhang, G.; Liu, T.; Giri, R.; Yu, J. –Q. J. Am. Chem. Soc. 2014, 136,
16940. (e) Chen, G.; Shigenari, T.; Jain, P.; Zhang, Z.; Jin, Z.; He, J.; Li S.; Mapelli, C.; Miller, M. M.; Poss, M. A.; Scola, P. M.; Yeung, K. ꢀS.; Yu, J. ꢀQ. J. Am. Chem. Soc. 2015, 137, 3338.
15 Racemization in the Stille coupling of a similar substrate has been observed at temperatures above 70 °C.
16 The coupling between benzo[b]thiophene 1a and 4ꢀiodotoluene 2a was tested using the standard conditions in the presence of additives bearing nitrile and amine groups. The desired product 3aa was
obtained in yields of only 6 ꢀ7% when benzonitrile (20 mol %), N,Nꢀdimethylaniline (20 mol %), morpholine (20 mol %) or succinonitrile (10 mol %) were added.
17 Kim, Y.ꢀJ.; Osakada, K.; Takenaka, A.; Yamamoto, A. J. Am. Chem. Soc. 1990, 112, 1096.
18 (a) Fors, B. P.; Buchwald, S. L. J. Am. Chem. Soc. 2009, 131, 12898. (b) Vinogradova, E. V.; Fors, B. P.; Buchwald, S. L. J. Am. Chem. Soc. 2012, 134, 11132.
19 Amatore, C.; Pfluger, F. Organometallics 1990, 9, 2276–2282.
20 (a) Shabashov, D.; Daugulis, O. Org. Lett. 2006, 8, 4947. Some Ruꢀmediated arylations have also shown this reactivity pattern. See: (b) Aihara, Y.; Chatani, N. Chem. Sci. 2013, 4, 664.
21 (a) Tang, S.ꢀY.; Guo, Q.ꢀX.; Fu, Y. Chem. Eur. J. 2011, 17, 13866. (b) Steinmetz, M.; Ueda, K.; Grimme, S.; Yamaguchi, J.; Kirchberg, S.; Itami, K.; Studer, A. Chem. Asian J. 2012, 7, 1256.
22 Conversely, a 1:6 reactivity ratio in favour of 1i was reported under Fagnou’s Cꢀ2 arylation conditions. See refs 6c and 7a.
23 There is often a correlation between pKa and reactivity under the CMD pathway, however, this is not necessarily the governing factor in reactivity. For a discussion, see: (a) Gorelsky, S. I.; Lapointe, D.;
Fagnou, K. J. Am. Chem. Soc. 2008, 130, 10848. (b) Gorelsky, S. I.; Lapointe, D.; Fagnou, K. J. Org. Chem. 2012, 77, 658.
24 (a) GómezꢀGallego, M.; Sierra, M. A. Chem. Rev. 2011, 111, 4857. (b) Simmons, E. M.; Hartwig, J. F. Angew. Chem. Int. Ed. 2012, 51, 3066.
25 (a) Reactions Rates of Isotopic Molecules; Melander, L.; Saunders, W. H.; Wiley: New York, 1980; pp 95. (b) Singleton, D. A.; Thomas, A. A. J. Am. Chem. Soc. 1995, 117, 9357.
26 For selected relevant examples of this technique, see: (a) Beno, B. R.; Houk, K. N.; Singleton, D. A. J. Am. Chem. Soc. 1996, 118, 9984. (b) Frantz, D. E.; Singleton, D. A.; Snyder, J. P. J. Am. Chem.
Soc. 1997, 119, 3383. (c) Singleton, D. A.; Szymanski, M. J. J. Am. Chem. Soc. 1999, 121, 9455. (d) Singleton, D. A.; Wang, Y.; Yang, H. W.; Romo, D. Angew. Chem. Int. Ed. 2002, 41, 1572.
27 Experimentally, R/R0 is approximated to the ratio of 13C with respect to an internal standard. This approximation is valid as long as the KIE for the internal standard is 1 and the proportion of 13C over
the total is small. See Ref 24a for the mathematical demonstration. In our case we selected C7 as the internal standard.
28 Vo, L. K.; Singleton, D. a. Org. Lett. 2004, 6, 2469.
29 1ꢀMethoxyꢀ3ꢀnitroꢀ4ꢀdeuterobenzene was used as an internal standard. For its synthesis, see: Grainger, R.; Nikmal, A.; Cornella, J.; Larrosa, I. Org. Biomol. Chem. 2012, 10, 3172.
30 Lapointe, D.; Fagnou, K. Chem. Lett. 2010, 39, 1118.
31 Groundꢀstate and transition state for the cycloaddition step were calculated by DFT using Gaussian. B3LYP and 6ꢀ31G(d) were used for mainꢀgroup atoms and LanL2DZ was used for Pd. See Supportꢀ
ing Information for details.
32 DFT modelling of the carbopalladiation step in 2,2,2ꢀtrifluoroethanol (TFE) and in 2ꢀmethylꢀ1ꢀpropanol (tBuOH) wew performed giving respectively free energy barriers of 22.0 kcal/mol and 21.7
kcal/mol.
33 KIEs were calculated according to Bigeleisen equations using ISOEFF: V. Anisinov, P. Paneth, ISOEFF98, Lodz, Poland, 1998. See supporting information for details, and: (a) Anisimov, V.; Paneth, P.
J. Math. Chem. 1999, 26, 75. For an example of use, see: (b) Cen, Y.; Sauve, A. A. J. Am. Chem. Soc. 2010, 132, 12286.
34 Calculations of KIEs were performed in gasꢀphase as they have been shown to be independent of basis set, solvent and functional within 4 orders of magnitude. For selected references see: (a) Hirschi, J. S.;
Takeya, T.; Hang, C.; Singleton, D. A. J. Am. Chem. Soc. 2009, 131, 2397; (b) Vetticatt, M. J.; Singleton, D. A. Org. Lett. 2012, 14, 2370.
35 DFT modelling of the CMD pathway in 2,2,2ꢀtrifluoroethanol (TFE) and in 2ꢀmethylꢀ1ꢀpropanol (tBuOH) were performed giving respectively free energy barriers of 28.5 kcal/mol and 29.2 kcal/mol.
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