Pleas Ce hd eo mni oc ta al dS j cu ise tn mc ea rgins
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ARTICLE
Chemical Science
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, 8214; d) F. Toulgoat, S. Alazet, T. Billard, Eur. J. Org.
Chem. 2014, 2415.
2 a) G. Teverovskiy, D. S. Surry, S. L. Buchwald, Angew. Chem. 23 S. Scheiblich, T. Maier, H. Baltruschat, PCT Int. Appl. (2001),
Int. Ed. 2011, 50, 7312; b) C.-P. Zhang, D. A. Vicic, J. Am. 41 pp. CODEN:PIXXD2; WO 01/36410A1
Chem. Soc. 2012, 134, 183; c) Z. Weng, W. He, C. Chen, R. 24 For a review, see: A. Y. Sizov, A. N. Kovregin, A. F. Ermolov,
Lee, D. Tan, Z. Lai, D. Kong, Y. Yuan, K.-W. Huang, Angew. Russ. Chem. Rev. 2003, 72, 357.
Chem. Int. Ed. 2013, 52, 1548; d) J. Xu, X. Mu, P. Chen, J. Ye, 25 Y. Huang, J. Ding, C. Wu, H. Zheng, Z. Weng, J. Org. Chem.
G. Liu, Org. Lett., 2014, 16, 3942; e) G. Yin, I. Kalvet, U. 2015, 80, 2912.
Englert, F. Schoenebeck, J. Am. Chem. Soc. 2015, 137, 4164; 26 M. Rueping, N. Tolstoluzhsky, P. Nikolaienko, Chem. Eur. J.
DOI: 10.1039/C5SC03359D
7540.
1
f) G. Yin, I. Kalvet, F. Schoenebeck, Angew. Chem. Int.
Ed. 2015, 54, 6809.
3 a) C. Chen, Y. Xie, L. Chu, R.-W. Wang, X. Zhang, F.-L. Qing,
2013, 19, 14043.
27 PhCN was also added. For the beneficial effect of nitrile, see:
1
1
Angew. Chem. Int. Ed. 2012, 51, 2492; b) C.-P. Zhang, D. A. 28 J. Högermeier, H.-U. Reissig, Adv. Synth. Catal. 2009, 351
Vicic Chem. Asian J. 2012, , 1756; c) X. Shao, X. Wang, T. 2747.
Yang, L. Lu, Q. Shen Angew. Chem. Int. Ed. 2013, 52, 3457; d) 29 For examples of superiority of nonaflates: a) S. Bräse, A. de
,
7
R. Pluta, P. Nikolaienko, M. Rueping, Angew. Chem. Int. Ed.
014, 53, 1650; e) Q. Glenadel, S. Alazet, A. Tlili, T. Billard,
Meijere, Angew. Chem. Int. Ed. 1995, 34, 2545; b) K. Voigt, P.
von Zezschwitz, K. Rosauer, A. Lansky, A. Adams, O. Reiser, A.
de Meijere, Eur. J. Org. Chem. 1998, 152; c) A. E. Jensen, W.
Dohle, P. Knochel, Tetrahedron 2000, 56, 4197; d) G. Dunet,
P. Knochel, Synlett 2006, 407.
2
Chem. Eur. J. 2015, 21, 14694.
4 For examples of metal-catalyzed C-H trifluoromethyl-
thiolation of arenes, see: a) L. D. Tran, I. Popov, O. Daugulis,
J. Am. Chem. Soc. 2012, 134, 18237; b) C. Xu, Q. Shen, Org. 30 The total time necessary for optimization, frequency and
Lett. 2014, 16, 2046.
5 J. Zakzeski, P. C. A. Bruijnincx, A. L. Jongerius, B. M.
Weckhuysen, Chem. Rev. 2010, 110, 3552.
energy calculation of the oxidative addition TSs was in
average 11.5 h (using 6 cores and 10GB memory on a MPI-S
node of the RWTH Bull cluster).
1
1
6 For precedence of aryl sulfide cleavage under Ni-catalysis,
see: a) S. Kanemura, A. Kondoh, H. Yorimitsu, K. Oshima,
Synthesis 2008, 2659; b) K. Lee, C. M. Counceller, J. P.
Stambuli, Org. Lett. 2009, 11, 1457; c) L. Melzig, A. Metzger,
P. Knochel, Chem. Eur. J. 2011, 17, 2948; d) N. Barbero, R.
Martin, Org. Lett. 2012, 14, 796.
1
1
7 Gaussian 09, Revision D.01, Frisch, M. J. et al. [see SI for full
reference]. The geometries were optimized in the gas-phase
at B3LYP/6-31G(d) with LANL2DZ (for Ni, Fe).
8 For appropriateness of method, see: a) T. Sperger, I. A.
Sanhueza, I. Kalvet, F. Schoenebeck, Chem. Rev. 2015, 115
,
9
532; b) M. T. Haynes, P. Liu, R. D. Baxter, A. J. Nett, K. N.
1
2
For reviewes, see: (a) Tamaru, Y. in Modern Organonickel Che mistry, Wiley-VCH, Weinheim, 2005. (b) Jana, R.; Pathak, T. P.; Sigman, M. S. Chem. Rev. 2011, 111, 1417-1492. (c) Han, F.-S. Chem. Soc. Rev. 2013, 42, 5270-5298. (d) Montgomery, J. “Organonickel Chemistry” in Organometallics in Synthesis: Fourth Manual Lipshutz, B. H. (Ed.) Wiley, H oboken, N.J., 2013, pp. 319-428.
Seechurn, C. C. J.; itching, M. O. Colacot, T. J. Snieckus, V. Ange w. Chem. Int. Ed. 2012, 1, 5062-5085.
K
;
5
3
Examples of Ni-catalyzed C-F activation: (a) Braun, T.; Foxon, S. P.; Perutz, R. N.; Walton, P. H. Angew. Chem. Int. Ed. 1999, 38, 3326-3329. (b) L. Ackermann, R. Born, J. H. Spatz, D. Meyer, Angew. Chem. Int. Ed. 2005,
For an overview, see: S. Z. Tasker, E. A. Standley, T. F. Jamison, Nature 2014,
509, 299.
4
4, 7216; (c) Johnson, S. A.; Huff, C. W.; Ferheen Mustafa, F.; Saliba, M. J. Am. Chem. Soc. 2008, 130, 17278-17280. (d) Tobisu, M.; Xu, T.; Shimasaki, T.; Chatani, N. J. Am. Chem. Soc. 2011, 133, 19505-19511.
5
For examples, see: (a) J. W. Dankwardt, Angew. Chem. Int. Ed. 2004, 43, 2428; (b) M. Tobisu, T. Shimasaki, N. Chatani,
Houk, J. Montgomery, J. Am. Chem. Soc. 2014, 136, 17495; c)
Angew.
Chem., Int. Ed., 2008, 47, 4866; (c) B.-T. Guan, S.-K. Xiang, T. Wu, Z.-P. Sun, B.- Q. Wang, K.- Q. Zhao and
T. Mesganaw, A. L. Silberstein, S. D. Ramgren, N. Fine Nathel,
Z.-J. Shi, Chem. Commun., 2008, 1437; (d) P. Alvarez-Bercedo, R. Martin, J. Am. Che m. Soc. 2010, 132, 17352; (e) A. G. Sergeev, J. F. Hartwig, Science 2011, 332, 439; (f) M. Tobisu, K. Yamakawa, T. Shimasaki and N. Chatani, Chem. Commun., 2011, 47, 2946; (g) A. G. Sergeev, J. D. Webb and J. F. Hartwig, J. Am. Chem. Soc., 2012, 134, 20226; (h) Ehle, A. R.; Zhou, Q.; Watson, M. P. O rg. Lett. 2012, 14, 1202-1205; (i) Muto, K.; Yamaguchi, J.; Lei, A.; Itami, K. J. Am. Chem. Soc. 2013, 135, 16384-16387. (j) Hoshimoto, Y.; Yabuki, H. J.; Kumar, R.; Suzuki, H.; Ohashi, M.; Ogoshi, S. J.
Am. Chem. Soc. 2014, 136 16752-16755.
X. Hong, P. Liu, N. K. Garg, Chem. Sci. 2011,
2
, 1766; d) see
,
(
I)
1
2
2
9 For mechanistic support of Ni as catalyst in C-O cleavage,
see: J. Cornella, E. Gomez-Bengoa, R. Martin, J. Am. Chem.
Soc. 2013, 135, 1997.
Pivalate coupling: K. W. Quasdorf, X. Tian, N. K. Garg, J. Am. Chem. Soc. 2008, 130, 14422
6
D
d) Fu-She Han, Chem. Soc. Rev. 2013, 42, 5270; c) R. Jana, T. P. Pathak, M. S. Sigman, Chem. Rev. 2011, 111, 1417;
7
8
For recent reviews on combining experiment and computation, see: (a) G.-J. Cheng, X . Zhang, L. W. Chung, L. Xu, Y.-D. Wu, J. Am. Chem. Soc. 2015, 137, 1706; (b) K. J. Bonney, F. Schoenebeck, Chem. Soc. Rev. 2014, 43, 6609; (c) A. S.-K. Tsang, I. A. Sanhueza, F. Schoenebeck, Chem. Eur. J. 2014, 20, 16432
9
For examples of
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nterests and activities to introduce fluorine containing group
8, 865 b) C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91, 165.
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;
b) P. Chen,
G
.
Liu, Synthesis 2013,
4
5, 2919
;
c) T. Liang, C. N. Neumann, T. Ritter, Angew. Chem. Int. Ed. 2013,
012, 134, 183.[c]
5
2, 8214
;
d) F. Toulgoat, S. Alazet, T. Billard,
Eur. J. Org. Chem. 2014, 2415.
1
2
[a]
d. 2015 54, 6809.
G. Teverovskiy, D. S. Surry, S. L. Buchwald, Angew. Chem. Int
.
Ed. 2011, 50, 7312.
[b]
C.-P. Zhang, D. A. Vicic, J. Am. Chem. Soc.
2
G. Yin, I. Kalvet, U.
E
nglert, F. Schoenebeck, J. Am. Chem. Soc. 2015, 10.1021/jacs.5b00538. [d]
Z. Weng, W. He, C. Chen, R. Lee, D. Tan, Z. Lai, D. Kong, Y. Yuan, K.-W. Huang, Angew. Chem. Int.
E
d. 2013
,
52, 1548. [e]
J. Xu, X. Mu, P. Chen, J. Ye, G. Liu, O rg. Lett., 2014, 16, 3942.
(
f) G. Yin, I. Kalvet, F. Schoenebeck, Angew. Chem. Int.
E
,
13
a) C. Chen, Y.
X
ie, L. Chu, R.-W. Wang, X. Zhang, F.-L. Qing, Angew. Chem. Int. Ed. 2012, 51,
2
492; b) C.-P. Zhang, D. A.
V
icic Chem. Asian J. 2012, 7,
1
756; c) X. Shao, X. Wang, T. Yang, L. Lu, Q. Shen Angew. Chem. Int. Ed. 2013, 52, 3457; d) R. Pluta, P. Nikolaienko, M. Rueping, Angew. Chem. Int. Ed. 2014, 53, 1650.
16, 2046.
1
45 For examples of metal-catalyzed C-H trifluoromethylthiolation of arenes, see: g) L. D. Tran, I. Popov, O. Daugulis, J. Am. Chem. Soc.
2
012, 134, 18240; h) C. Xu, Q. Shen, Org. Lett. 2014,
J. Zakzeski, P. C. A. Bruijnincx, A. L. Jongerius, B. M. Weckhuysen, Chem. Rev. 110, 3552 (2010).
(
I)
0 Using 10 mol% of [(dppf)Ni (Cl)] complex as catalyst for the
trifluoromethylthiolation of PhOTf with (Me N)(SCF ) at 45°C
16
For precedence of aryl sul fide cleavage under Ni-catalysis, see: (a) Kanemura, S.; Kondoh, A.; Yorimitsu, H.; Oshima, K. Synthesis 2008, 2659- 2664. (b) Lee, K.; Counceller, C. M.; Stambuli, J. P. Org. Lett. 2009, 11, 1457-1459. (c) Melzig, L.; Metzger, A.; Knochel, P. Chem. Eur. J. 2011, 17, 2948-2956. (d) Barbero, N.; Martin, R. Org. Lett. 2012, 14, 796- 799.
4
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12 We did not consider influence of other substituents
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first general assessment for most likely wide and general scope. It is likely, that specialized substrates with electronic bias may also allow for selected examples of these functional groups to be converted. The goal of this assessment w as to identify compatible functionality that would allow for w idest possible scope.
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For a review, see: A. Y. Sizov, A. N. Kovregin, A. F. Ermolov, Russ. Che m. Rev. 2003, 72, 357
1 We did not consider the influence of other substituents or
alternative mechanisms on this trend. It is likely, that
specialized substrates with electronic bias may also allow for
selected examples of these functional groups to be
converted. The goal of this assessment was to identify
compatible functionality that would allow for widest possible
scope in the context of [Ni(0)] catalysis.
[a]
Zhang, C.-P.; Vicic, D. A. Chem.
-
Asian J. 2012, 7, 1756–1758; [b]
Huang, Y.; Ding, J.; Wu, C.; Zheng, H.; Weng, Z.; J. Org. Chem., 2015, 80, 2912–2917
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Zheng, Z.-H. Wu, Z.-J. Shi, Org. Lett. 2009, 11, 3374; c) J.-S.
6
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