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ACS Catalysis
Wu, C.; Zeng, X. Org. Lett. 2014, 16, 2248-2251. (h) Gou, Q.;
M.; Urbano, A. Chem. Commun. 2009, 45, 6129-6144. (b) Sipos,
G.; Drinkel, E. E.; Dorta, R. Chem. Soc. Rev. 2015, 44, 3834-3860.
(c) Trost, B. M.; Rao, M. Angew. Chem., Int. Ed. 2015, 54, 5026-
5043.
1
2
3
4
5
6
7
8
9
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
Zhang, Z.-F.; Liu, Z.-C.; Qin, J. J. Org. Chem. 2015, 80, 3176-3186.
(i) Chen, G.; Gong, W.; Zhuang, Z.; S.Andrä, M.; Chen, Y.-Q.;
Hong, X.; Yang, Y.-F.; Liu, T.; Houk, K. N.; Yu, J.-Q. Science 2016,
353, 1023-1027.
14 For selected examples of sulfoxide ligands for Pd-catalyzed C-H
functionalization reactions: (a) Chen, M. S.; White, M. C. J. Am.
Chem. Soc. 2004, 126, 1346-1347. (b) Covell, D. J.; White, M. C.
Angew. Chem., Int. Ed. 2008, 47, 6448-6451. (c) Yamaguchi, K.;
Hondo, H.; Yamaguchi, J.; Itami. K. Chem. Sci. 2013, 4, 3753-3757.
(d) Kondo, H.; Yu, F.; Yamaguchi, J.; Liu, G.; Itami. K. Org. Lett.
2014, 16, 4212-4215.
15 Compound 31 was prepared in high yield via H2O2 oxidation of 25.
(see Supporting Information)
16 Use of HFIP solvent did not improve the AQ- or TA-directed C-H
arylation reactions listed in Scheme 2. See Supporting Information
for more details.
17 For a discussion on the use of fluorinated alcohols as solvents in
metal catalyzed C-H functionalization reactions, see: Wencel-
Delord, J.; Colobert, F. Org. Chem. Front. 2016, 3, 394-400.
18 Hameed, A.; Alharthy, R. D.; Iqbal, J.; Langer, P. Tetrahedron 2016,
72, 2763-2812.
19 For selected reviews on structure and bonding in metal sulfoxide
complexes see: (a) Davies, J. A. Adv. Inorg. Chem. Radiochem. 1981,
24, 115-187. (b) Calligaris, M.; Carugo, O. Coord. Chem. Rev. 1996,
153, 83-154. (c) Calligaris, M. Coord. Chem. Rev. 2004, 248, 351-
375.
20 For studies on π backbonding interactions between sulfoxide lig-
ands and Ru or Ir: (a) Stener, M.; Calligaris, M. J. Mol. Chem. (The-
ochem) 2000, 497, 91-104. (b) Evans, D. R.; Huang, M.; Seganish,
W. M.; Fettinger, J. C.; Williams, T. L. Inorg. Chem. Commun. 2003,
6, 462-465.
21 For a computational study of π backbonding interactions between
sulfoxide and Pd: Xu, Z.-G.; Gu, G.-B.; Liu, H.-Y. Chin. J. Inorg.
Chem. 2007, 23, 785-790. The results suggest that di-phenyl sulfox-
ide has a stronger π-backbonding interaction with Pd(II) than di-
hexyl sulfoxide.
22 We were unsuccessful in our attempts to obtain an X-ray structure
of 79. The IR spectrum of 79 indicates an increase in the SO
stretching frequency (~ 80 cm-1), compared to the IR spectrum of
78. The binding of sulfoxide ligands to a metal center through a sul-
fur atom typically causes a decrease in the S-O bond length and an
increase of its stretching frequencies in IR spectroscopy. For select-
ed studies on IR of palladium sulfoxide complex see: (a) Price, J. H.;
Williamson, A. N.; Schramm, R. F.; Wayland, B. B. Inorg. Chem.
1972, 11, 1280-1284. (b) Diao, T.; White, P.; Guzei, I.; Stahl, S. S.
Inorg. Chem. 2012, 51, 11898-11909. (c) Drinkel, E. E.; Wu, L.;
Linden, A.; Dorta, R. Organometallics 2014, 33, 627-636. (d) To-
kunoh, R.; Sodeoka, M.; Aoe, K.; Shibasaki, M. Tetrahedron Lett.
1995, 36, 8035-8038.
23 For examples of Pd-catalyzed stereoselective arylation of methylene
C(sp3)–H bonds using enantioenriched auxiliaries: (a) Chen, K.;
Li, Z.-W.; Shen, P.-X.; Zhao, H.-W.; Shi, Z.-J. Chem. Eur. J. 2015,
21, 7389-7393. (b) Kim, J.; Sim, M.; Kim, N.; Hong, S. Chem. Sci.
2015, 6, 3611-3616. (c) Ling, P.-X.; Fang, S.-L.; Yin, X.-S.; Chen,
K.; Sun, B.-Z.; Shi, B.-F. Chem. Eur. J. 2015, 21, 17503-17507.
4
For selected examples of Pd-catalyzed methylene C(sp3)-H aryla-
tion of cyclic alkyl carboxamides: (a) Wasa, M.; Engle, K. M.; Lin,
D. W.; Yoo, E. J.; Yu, J.-Q. J. Am. Chem. Soc. 2011, 133, 19598-
19601. (b) Gutekunst, W. R.; Baran, P. S. J. Am. Chem. Soc. 2011,
133, 19076-19079. (c) Gutekunst, W. R.; Gianatassio, R.; Baran, P.
S. Angew. Chem., Int. Ed. 2012, 51, 7507-7510. (d) Parella, R.; Go-
palakrishnan, B.; Babu, S. A. J. Org. Chem. 2013, 78, 11911-11934.
(e) Parella, R.; Gopalakrishnan, B.; Babu, S. A. Org. Lett. 2013, 15,
3238-3241. (f) Gutekunst, W. R.; Baran, P. S. J. Org. Chem. 2014,
79, 2430-2452. (g) Ting, C. P.; Maimone, T. J. Angew. Chem., Int.
Ed. 2014, 53, 3115-3119. (h) Affron, D. P.; Davis, O. A.; Bull, J. A.
Org. Lett. 2014, 16, 4956-4959. (i) Parella, R.; Babu, S. A. J. Org.
Chem. 2015, 80, 2339-2355. (j) Feng, R.; Wang, B.; Liu, Y.; Liu, Z.;
Zhang, Y. Eur. J. Org. Chem. 2015, 142-151. (k) Nack, W. A.; Wang,
B.; Wu, X.; Jiao, R.; He, G.; Chen, G. Org. Chem. Front. 2016, 3,
561-564. (l) Topczewski, J. J.; Cabrera, P. J.; Saper, N. I.; Sanford,
M. S. Nature 2016, 531, 220-224.
5
Examples of Pd-catalyzed arylation of unactivated C(sp3)–H bonds
with aryl iodides bearing ortho substituents: (a) Wasa, M.; Engle, K.
M.; Yu, J.-Q. J. Am. Chem. Soc. 2009, 131, 9886-9887. (b) He, J.; Li,
S.; Deng, Y.; Fu, H.; Laforteza, B. N.; Spangler, J. E.; Homes, A.; Yu,
J.-Q. Science 2014, 343, 1216-1220. (c) Chen, K.; Zhang, S.-Q.; Xu,
J.-W.; Hu, F.; Shi, B.-F. Chem. Commun. 2014, 50, 13924-13927. (d)
Liu, J.; Xie, Y.; Zeng, W.; Lin, D.; Deng, Y.; Lu, X. J. Org. Chem.
2015, 80, 4618-4626.
For rare examples of high-yielding Pd-catalyzed C–H arylation with
2-iodotoluene 4, see: (a) Gong, W.; Zhang, G.; Liu, T.; Giri, R.; Yu,
J.-Q. J. Am. Chem. Soc. 2014, 136, 16940-16946. (b) Zhang, S.-K.;
Yang, X.-Y.; Zhao, X.-M.; Li, P.-X.; Niu, J.-L.; Song, M.-P. Organo-
metallics 2015, 34, 4331-4339.
During the preparation of this manuscript, a related Pd-catalyzed
asymmetric C(sp3)-H arylation of small cycloalkanes using sulfinyl
aniline auxiliaries was reported: Jerhaoui, S.; Chahdoura, F.; Rose,
C.; Djukic, J.; Wencel-Delord, J.; Colobert, F. Chem. Eur. J. 2016,
22, 17397-17406.
He, G.; Zhang, S.-Y.; Nack, W. A; Pearson, R.; Rabb-Lynch, J.;
Chen, G. Org. Lett. 2014, 16, 6488-6491.
6
7
8
9
Zhang, X.; He, G.; Chen, G. Org. Biomol. Chem. 2016, 14, 5511-
5515.
10 (a) Zaitsev, V. G.; Shabashov, D.; Daugulis, O. J. Am. Chem. Soc.
2005, 127, 13154-13155. (b) Shabashov, D.; Daugulis, O. J. Am.
Chem. Soc. 2010, 132, 3965-3972. (c) Tran, L. D.; Daugulis, O. An-
gew. Chem., Int. Ed. 2012, 51, 5188-5191.
11 For a recent review on sulfoxide-directed C-H functionalization:
Pulis, A. P.; Procter, D. J. Angew. Chem., Int. Ed. 2016, 55, 9842-
9860.
12 For selected examples of metal-catalyzed sulfoxide-directed C-H
functionalization: (a) Coulter, M. M.; Dornan, P. K.; Dong, V. M. J.
Am. Chem. Soc. 2009, 131, 6932-6933. (b) Wesch, T.; Berthelot-
Bréhier, A.; Leroux, F. R.; Colobert, F. Org. Lett. 2013, 15, 2490-
2493. (c) Wesch, T.; Leroux, F. R.; Colobert, F. Adv. Synth. Catal.
2013, 355, 2139-2144. (d) Wang, B.; Shen, C.; Yao, J.; Yin, H.;
Zhang, Y. Org. Lett. 2014, 16, 46-49. (e) Wang, B.; Liu, Y.; Lin, C.;
Xu, Y.; Liu, Z.; Zhang, Y. Org. Lett. 2014, 16, 4574-4577. (f) No-
bushige, K.; Hirano, K.; Satoh, T.; Miura, M. Org. Lett. 2014, 16,
1188-1191. (g) Padala, K.; Jeganmohan, M. Chem. Commun. 2014,
50, 14573-14576. (h) Hazra, C. K.; Dherbassy, Q.; Wencel-Delord,
J.; Colobert, F. Angew. Chem., Int. Ed. 2014, 53, 13871-13875. (i)
Dherbassy, Q.; Schwertz, G.; Chessé, M.; Hazra, C. K.; Wencel-
Delord, J.; Colobert, F. Chem. Eur. J. 2016, 22, 1735-1743. (j) Col-
lins, B. S. L.; Kistemaker, J. C. M.; Otten, E.; Feringa, B. L. Nat.
Chem. 2016, 8, 860-866.
13 For selected reviews on chiral sulfoxide ligands in asymmetric catal-
ysis, see: (a) Carreño, M. C.; Hernández-Torres, G.; Ribagorda,
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