ACS Catalysis
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1
2
3
4
5
6
7
8
9
Garg, N. K. Angew. Chem. Int. Ed. 2016, 55, 15129–15132. i)
2013, 17, 29−39. d) Ananikov, V. P. ACS Catal. 2015, 5,
1964−1971.
Dey, A.; Sasmal, S.; Seth, K.; Lahiri, G. K.; Maiti, D. ACS Catal.
2017, 7, 433–437. j) Ni, S.; Zhang, W.; Mei, H.; Han, J.; Pan, Y.
Org. Lett. 2017, 19, 2536–2539. k) Medina, J. M.; Moreno, J.;
Racine, S.; Du, S.; Garg, N. K. Angew. Chem. Int. Ed. 2017, 56,
6567–6571. l) Hu, J.; Wang, M.; Pu, X.; Shi, Z. Nat. Com-
mun. 2017, 8, 14993–14999. m) Weires, N. A.; Caspi, D. D.;
Garg, N. K. ACS Catal. 2017, 7, 4381–4385. n) Shi, S.; Szostak,
M. Synthesis 2017, 49, 3602–3608. o) Dander, J. E.; Baker, E. L.;
Garg, N. K. Chem. Sci. 2017, 8, 6433–6438. p) For a recent re-
view, see: Dander, J. E.; Garg, N. K. ACS Catal. 2017, 7, 1413–
1423.
9 Amani, J.; Alam, R.; Badir, S.; Molander, G. A. Org. Lett. 2017,
19, 2426–2429.
10 Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815–
3818.
11 As Molander’s methodology utilizes alkyl boron reagents (see
ref 9), and ours uses aryl boron reagents, the two methods offer
different strategic approaches to access ketone products.
12 The less activated N-Bn,Boc amides used in the present study
are not competent substrates in the Ir/Ni photoredox-mediated
couplings of N-acyl succinimides (see ref 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
5 For nickel-catalyzed decarbonylative coupling reactions of am-
ides, see: a) Shi, S.; Meng, G.; Szostak, M. Angew. Chem. Int. Ed.
2016, 55, 6959–6963. b) Hu, J.; Zhao, Y.; Liu, J.; Zhang, Y.; Shi,
Z. Angew. Chem. Int. Ed. 2016, 55, 8718–8722. c) Srimontree,
W.; Chatupheeraphat, A.; Liao, H.-H.; Rueping, M. Org. Lett.
2017, 19, 3091–3094. d) Liu, C.; Szostak, M. Angew. Chem. Int.
Ed. 2017, 56, 12718–12722. e) Yue, H.; Guo, L.; Liao, H.-H.;
Cai, Y.; Zhu, C.; Rueping, M. Angew. Chem. Int. Ed. 2017, 56,
4282–4285. f) Chatupheeraphat, A.; Liao, H.-H.; Lee, S.-C.;
Rueping, M. Org. Lett. 2017, 19, 4255–4258. g) Yue, H.; Guo, L.;
Lee, S.-C.; Liu, X.; Rueping, M. Angew. Chem. Int. Ed. 2017, 56,
3972–3976. h) Hu, J.; Wang, M.; Pu, X.; Shi, Z. Nat. Commun.
2017, 8, 14993–14999.
13 a) Gooßen, L. J.; Ghosh, K. Angew. Chem. Int. Ed. 2001, 40,
3458–3460. b) Gooßen, L. J.; Ghosh, K. Eur. J. Org. Chem. 2002,
3254–3257. c) Yang, H.; Li, H.; Wittenberg, R.; Egi, M.; Huang,
W.; Liebeskind, L. S. J. Am. Chem. Soc. 2007, 129, 1132–1140.
d) Lovell, K. M.; Vasiljevik, T.; Araya, J. J.; Lozama, A.; Prevatt-
Smith, K. M; Day, V. W.; Dersch, C. M.; Rothman, R. B.; Butel-
man, E. R.; Kreek, M. J.; Prisinzano, T. E. Bioorg. Med. Chem.
2012, 20, 3100–3110. e) Haddach, M.; McCarthy, J. R. Tetrahe-
dron Lett. 1999, 40, 3109–3112. f) Nique, F.; Hebbe, S.; Tribal-
leau, N.; Peixoto, C.; Lefrancois, J.-M.; Jary, H.; Alvey, L.; Man-
ioc, M.; Housseman, C.; Klaassen, H.; Van Beeck, K.; Guedin,
D.; Namour, F.; Minet, D.; Van Der Aar, E.; Feyen, J.; Fletcher,
S.; Blanque, R.; Robin-Jagerschmidt, C.; Deprez, P. J. Med.
Chem. 2012, 55, 8236–8247.
6 For palladium-catalyzed C–C bond forming reactions of amides,
see: a) Li, X.; Zou, G. Chem. Commun. 2015, 51, 5089–5092. b)
Yada, A.; Okajima, S.; Murakami, M. J. Am. Chem. Soc. 2015,
137, 8708–8711. c) Meng, G.; Szostak, M. Org. Biomol. Chem.
2016, 14, 5690–5705. d) Meng, G.; Szotak, M. Angew. Chem. Int.
Ed. 2015, 54, 14518–14522. e) Meng, G.; Szostak, M. Org. Lett.
2015, 17, 4364–4367. f) Liu, C.; Meng, G.; Liu, Y.; Liu, R.; La-
lancette, R.; Szostak, R.; Szostak, M. Org. Lett. 2016, 18, 4194–
4197. g) Lei, P.; Meng, G.; Szostak, M. ACS Catal. 2017, 7,
1960–1965. h) Liu, C.; Liu, Y.; Liu, R.; Lalancette, R.; Szostak,
R.; Szostak, M. Org. Lett. 2017, 19, 1434–1437. i) Liu, C.; Meng,
G.; Szostak, M. J. Org. Chem. 2016, 81, 12023–12030. j) Meng,
G.; Shi, S.; Szostak, M. ACS Catal. 2016, 6, 7335–7339. k) Cui,
M.; Wu, H.; Jian, J.; Wang, H.; Liu, C.; Stelck, D.; Zeng, Z.
Chem. Commun. 2016, 52, 12076–12079. l) Wu, H.; Li, Y.; Cui,
M.; Jian, J.; Zeng, Z. Adv. Synth. Catal. 2016, 358, 3876–3880.
m) Shi, S.; Szostak, M. Org. Lett. 2017, 19, 3095–3098. n) Lei,
P.; Meng, G.; Ling, Y.; An, J.; Szostak, M. J. Org. Chem. 2017,
82, 6638–6646. o) Meng, G.; Szostak, R.; Szostak, M. Org. Lett.
2017, 19, 3596–3599. p) Meng, G.; Lalancette, R.; Szostak, R.;
Szostak, M. Org. Lett. 2017, 19, 4656–4659. q) Osumi, Y.; Szos-
tak, M. Org. Biomol. Chem. 2017, 15, 8867–8871. r) Lei, P.;
Meng, G.; Ling, Y.; An, J.; Nolan, S. P.; Szostak, M. Org. Lett.
2017, DOI: 10.1021/acs.orglett.7b03191.
14 The N-Bn,Boc amide derivatives employed in this study can be
readily prepared from the corresponding carboxylic acids (i.e.,
benzyl amide formation, followed by treatment with Boc2O) or
directly from acid chlorides (i.e., using HN(Bn)Boc).
15
For use of the Ni/ICy system in the Stille coupling of quater-
nary ammonium salts, see: Wang, D.-Y.; Kawahata, M.; Yang, Z.-
K.; Miyamoto, K.; Komagawa, S.; Yamaguchi, K.; Wang, C.;
Uchiyama, M. Nat. Commun. 2016, 7, 12937–12945.
16 We attribute the improved competency of ligand 10 to its elec-
tron-rich nature, which ultimately renders oxidative addition more
facile. For discussion of NHC ligands in transition metal catalysis,
see: Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F.
Nature 2014, 510, 485–496.
17 For the relative nucleophilicities of substituted aryl boronates,
see: a) Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald,
S. L.; J. Am. Chem. Soc. 2005, 127, 4685–4696. b) Billingsley, K.
L.; Buchwald, S. L. Angew. Chem. Int. Ed. 2008, 47, 4695–4698.
18 The underpinnings behind the modest catalyst turnover (i.e.,
Figure 5, entries 2 and 3) is not presently understood.
19 In addition to esters, ketones, tertiary alcohols, secondary ami-
des, carboxylic acids, and epoxides are tolerated in this methodo-
logy, as determined by a robustness screen; see the SI for details.
20 For bioactive spiroindolenines, see: a) Weisbach, J. A.; Macko,
E.; De Sanctis, N. J.; Cava, M. P.; Douglas, B. J. Med. Chem.
1964, 7, 735–739. b) Fourtillan, J.-B.; Violeau, B.; Karam, O.;
Jouannetaud, M.-P.; Fourtillan, M.; Jacquesy, J.-C. Melatoniner-
gic Agonist Spiro[indolepyrrolidine] Derivatives, Process for
Their Preparation and Their Use as Medicinal Products, 1998,
US576347. c) Chowdhury, S.; Fu, J.; Liu, S.; Qi, J. Spiro-
Condensed Indole Derivatives as Sodium Channel Inhibitors,
2010, WO2010/53998. d) Li, X.-N.; Cai, X.-H.; Feng, T.; Li, Y.;
Liu, Y.-P.; Luo, X.-D. J. Nat. Prod. 2011, 74, 1073–1078. e) Xu,
Y.-J.; Pieters, L. Mini. Rev. Med. Chem. 2013, 13, 1056–1072. f)
Sweis, R. F.; Pliushchev, M.; Brown, P. J.; Guo, J.; Li, F.; Maag,
D.; Petros, A. M.; Soni, N. B.; Tse, C.; Vedadi, M.; Michaelides,
7
For examples of Pd-catalyzed Suzuki–Miyaura coupling of ali-
phatic amides, see: Li, X.; Zou, G. J. Organomet. Chem. 2015,
794, 136–145.
8 The field of nickel-catalyzed cross-couplings itself has gained
tremendous interest in recent years due not only to the high natu-
ral abundance, low cost, and low CO2 footprint of nickel, but also
because of its ability to effect new or challenging transformations,
including those involving activation of the amide C–N bond. For
pertinent reviews on nickel catalysis, see: a) Rosen, B. M.;
Quasdorf, K. W.; Wilson, D. A.; Zhang, N.; Resmerita, A.-M.;
Garg, N. K.; Percec, V. Chem. Rev. 2011, 111, 1346−1416. b)
Tasker, S. Z.; Standley, E. A.; Jamison, T. F. Nature 2014, 509,
299−309. c) Mesganaw, T.; Garg, N. K. Org. Process Res. Dev.
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