Synthesis of Benzoisoselenazolone Derivatives by Nickel-Catalyzed Dehydrogenative Direct Selenation of C(sp2)-H Bonds with Elemental Selenium in Air

Article abstract of DOI:10.1021/acs.orglett.7b00116

Nickel-catalyzed direct selenation of benzamides bearing an 8-quinolyl auxiliary with elemental selenium provides benzoisoselenazolones in good yield via carbon-selenium and nitrogen-selenium bond formation under aerobic conditions. In addition to aryl C-

Full text of DOI:10.1021/acs.orglett.7b00116

Letter
pubs.acs.org/OrgLett
Synthesis of Benzoisoselenazolone Derivatives by Nickel-Catalyzed
Dehydrogenative Direct Selenation of C(sp2)−H Bonds with
Elemental Selenium in Air
Masayuki Iwasaki,† Natsumi Miki,‡ Yuta Tsuchiya,‡ Kiyohiko Nakajima,§ and Yasushi Nishihara*,†
†Research Institute for Interdisciplinary Science, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan
‡Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan
§Department of Chemistry, Aichi University of Education, Igaya, Kariya 448-8542, Japan
S
* Supporting Information
ABSTRACT: Nickel-catalyzed direct selenation of benzamides
bearing an 8-quinolyl auxiliary with elemental selenium provides
benzoisoselenazolones in good yield via carbon−selenium and
nitrogen−selenium bond formation under aerobic conditions. In
addition to aryl C−H bonds, the method can also be applied to
alkenyl C−H bonds, constructing an isoselenazolone skeleton.
Simple mechanistic analysis shows that the reaction proceeds through a rate-determining C−H bond cleavage. The obtained
benzoisoselenazolones are transformed into various organoselenium compounds and utilized as the catalyst for
bromolactonization of alkenoic acids.
used as the starting compounds. One of the key steps in this
enzoisoselenazolones consisting of 5-membered hetero-
Bcycles having a nitrogen−selenium bond are attracting transformation was reported by Chatani and co-workers.11 They
found that the combination of nickel and an N,N′-bidentate
chelating group in the substrate can yield the direct
functionalization of benzamides. In addition, Hillhouse reported
the insertion of elemental selenium in nickelacycles, giving
selenium-containing heterocycles.12 If these two fundamental
reactions were aided by the use of a nickel catalyst, a powerful
synthetic method for benzoisoselenazolones could be estab-
lished. Although the chelate-assisted catalytic direct thiolation
and selenation of aryl C−H bonds with disulfides and diselenides
have been well developed,13−16 the reaction with elemental
selenium as an electrophilic reagent has yet to be reported.
Herein, we report the nickel-catalyzed oxidative direct selenation
of benzamides with elemental selenium. In addition, a reaction
pathway including the unprecedented single-electron oxidation
of a nickelacycle(II) intermediate in air is proposed.
increasing interest as biologically active molecules. The
representative compound ebselen and its derivatives have
occupied a central position in organoselenium chemistry for
some time. Ebselen is well-known to exhibit important
antioxidant activity, mimicking glutathione peroxidase,1 as well
as having other medically promising qualities.2 In addition, it was
found to be a safe treatment for bipolar disorder, superior by far
to the conventional drug, lithium.3 Moreover, ebselen and its
analogues have been used as catalysts for the oxidation of organic
compounds.4 Despite these fascinating properties, since their
derivatization has not been well investigated, the construction of
benzoisoselenazolone scaffolds is still challenging. Indeed, these
compounds have been synthesized by ortho-lithiation of
benzamides and subsequent annulation with selenium electro-
philes,5 annulation of o-chloroselanylbenzoyl chloride with
primary amines,6 or radical cyclization of diselenides or their
analogues.7,8 These multistep synthetic methods often gave low
overall yields, and the frequently harsh reaction conditions were
incompatible with many functional groups. Recently, Kumar
reported the copper-catalyzed annulation of o-halobenzamides
with elemental selenium.9 Although that reaction can be
conducted under mild conditions, expanding the substrate
scope to some extent, the preparation of the starting aryl halides
requires several tedious synthetic steps. Thus, there has been no
convenient general method for constructing the benzoisosele-
nazolone skeleton.
With the hypothetical mechanism described above in mind, we
first examined the reaction of benzamide 1a with elemental
selenium in the presence of the nickel catalyst. After extensive
screening of various reaction parameters, we were pleased to find
that direct selenation proceeded in the presence of Ni(OAc)2·
n
4H2O/PPh3 as a catalyst, sodium carbonate, and Bu4NCl in
DMF at 140 °C in atmospheric air to yield the desired
benzoisoselenazolone 2a in 93% yield (Scheme 1). Under an
argon atmosphere, the reaction provided 2a as much as the
n
catalyst loaded. The addition of Bu4NCl improved the yield
significantly, probably because the ammonium halide additive
might help elemental selenium to dissolve in organic solvents.17
In contrast, oxidative C−H functionalization has provided an
efficient synthetic method for various heterocycles.10 Therefore,
the synthesis of benzoisoselenazolones by oxidative direct
selenation would be desirable since simple benzamides can be
Received: January 13, 2017
© XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.7b00116
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Scheme 1. Optimal Conditions for Nickel-Catalyzed Direct
Selenation of Benzamide 1a with Elemental Selenium
Scheme 2. Nickel-Catalyzed Direct Selenation of Benzamides
and Acrylamides 1 with Elemental Selenium
a
Using DMF as the solvent was crucial for the efficiency of the
reaction. Other solvents gave poor results. The reaction had to be
performed at high temperature, as lower temperatures produced
lower yields. A detailed summary of the optimization process is in
the Supporting Information.
Continuous optimization proved that the reaction of 1a was
complete even at 120 °C when 2 equiv of elemental selenium was
employed. With the optimized conditions in hand, we sought to
demonstrate the generality of the direct selenation with
elemental selenium. As shown in Scheme 2, nonsubstituted
benzamide 1b also underwent the desired reaction to yield
benzoisoselenazolone 2b in 73% yield. A gram-scale direct
selenation of 1b on an 8 mmol scale was also achieved to provide
1.32 g of 2b albeit in a slightly lower yield of 51%. A wide variety
of functional groups were compatible under mild oxidative
conditions, including an electron-donating methoxy group (2c)
as well as electron-deficient trifluoromethyl (2d), cyano (2e),
and methoxycarbonyl (2f) groups. Moreover, benzamides
bearing chloro and bromo groups were also compatible with
our protocol, permitting further transformations of benzoisose-
lenazolones 2g and 2h using cross-coupling techniques.
Furthermore, a methyl substituent in the meta position of
benzamide directed aromatic C−H bond cleavage to a less
hindered ortho C−H bond (2i) with perfect selectivity. The
structure of 2i was unambiguously confirmed by X-ray diffraction
analysis.18 In addition to benzamides, acrylamides were also
readily accommodated under these reaction conditions. The
reactions of acrylamides 1j and 1k having either aliphatic or
aromatic substituents also gave the corresponding isoselenazo-
lones 2j and 2k. Additionally, acrylamide 1l not substituted at the
β-position could also be used in the present direct selenation
(2l). With respect to a directing group on a nitrogen atom of
benzamide, a 5-methoxy-substituted quinolyl group worked well
to provide 2m in 88% yield, while product 2n was not obtained
from 1n having a 1-naphthyl group. N,N′-Bidentate auxiliaries
were found to be essential for this direct selenation. In contrast,
the corresponding thiolation and telluration with elemental
sulfur and tellurium have not been successful to date, indicating
that further modification of reaction conditions must be needed.
Although we postulated that the reaction involves a chelate-
assisted C−H bond cleavage and the direct incorporation of
selenium, other alternative pathways cannot be ruled out, which
might include a direct chlorination19 of benzamide 1 with
ammonium chloride and the subsequent annulation of o-
chlorobenzamide with elemental selenium.9 In order to confirm
which pathway is operative, the identical reaction of 1b was
conducted without elemental selenium.20 This did not produce
the chlorinated product, while 1b was recovered quantitatively,
thus completely ruling out the direct chlorination pathway. It is
worth mentioning that no alkylated product was observed,
although ammonium halides are used as alkylating reagents
a
1, elemental selenium (2 equiv), Ni(OAc)2·4H2O (10 mol %), PPh3
n
(20 mol %), Na2CO3 (2 equiv), and Bu4NCl (3 equiv) in DMF (0.4
M) at 120 °C for 24 h. 12 h. 8 h Se (1.5 equiv). 140 °C, 12 h. 140
°C, 3 h Se (1.5 equiv).
b
c
d
e
under similar reaction conditions.21 To gain more insight into the
reaction mechanism, we next performed deuterium-labeling
experiments.20 Intramolecular competitive reaction using
deuterated benzamide provided a significant primary kinetic
isotope effect (KIE) of 2.5. Similar KIEs were obtained in parallel
experiments (2.4) and intermolecular competition (3.3). These
observations strongly suggest that C−H bond cleavage is the
rate-determining step of the reaction.22
Although the reaction mechanism of nickel-catalyzed oxidative
direct selenation remains unclear at this stage, a proposed
mechanism is illustrated in Scheme 3 on the basis of published
information and our experimental results. Initially, a base-
promoted ligand exchange between a nickel(II) precursor and 1b
gives a nickel complex A that then undergoes the rate-
determining cyclometalation to afford the azanickelacycle
intermediate B.11 The sequential insertion of elemental selenium
B
DOI: 10.1021/acs.orglett.7b00116
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Organic Letters
Letter
sodium borohydride, followed by aerobic treatment, yielded the
corresponding diselenide 4 in 95% yield. Moreover, 2b reacted
with p-toluenethiol to construct the selenium−sulfur bond in 5.
Furthermore, the reactions of 2b with benzoyl chloride and
trifluoromethylsilane respectively furnished aryl selenide de-
rivatives 6 and 7 in good yield. The prepared benzoisoselena-
zolone 2b was also found to act as an efficient catalyst for
bromolactonization of pentenoic acid with bromine.25 Although
the reaction gave the 5-exo-trig cyclized product in 35% yield
without any catalyst, the addition of even 1 mol % of 2b greatly
accelerated bromolactonization for an 85% yield of the
product.21
Scheme 3. Plausible Reaction Mechanism
In summary, we have developed chelate-assisted direct
selenation of aryl and alkenyl C−H bonds with elemental
selenium catalyzed by nickel, which provides a new synthetic
route to isoselenazolone derivatives. The present reaction was
employed under mild oxidative conditions to expand substrate
scope and shows excellent functional group compatibility.
Although the detailed mechanism remains to be investigated,
we tentatively propose that the reaction proceeds through the
unprecedented single-electron oxidation of the stable
nickelacycle(II) species in air. The synthetic utility of
benzoisoselenazolones was unambiguously demonstrated by
the further transformations, giving rise to valuable organo-
selenium compounds and the catalytic bromolactonization of
alkenoic acids.
into a carbon−nickel bond of B generates a 6-membered
nickelacycle C.12 Aerobic oxidation of nickel(II) species C to
complex D prompts smooth reductive elimination to provide
product 2b with the release of nickel(I) species.15h,23 The initial
nickel(II) species is regenerated by oxidation of the nickel(I)
complex in air to complete the catalytic cycle. The alternative
mechanism may involve reductive elimination from C, giving 2b
and a nickel(0) species that is oxidized in air to regenerate active
nickel(II). It is known that a six-membered selenanickelacycle
intermediate undergoes reductive elimination under an oxygen
atmosphere remarkably faster than under an inert gas.12 The
results imply that a high-valent nickel species is formed during
reductive elimination.24
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.orglett.7b00116.
More detailed results of nickel-catalyzed reactions and 1H,
13C{1H}, and 19F{1H} NMR spectra of the products
(PDF)
Synthetically versatile benzoisoselenazolones prepared by our
method could be readily converted to a variety of useful
organoselenium compounds (Scheme 4). For example, the
reaction of 2b with methylmagnesium iodide provided the ring-
opening product 3 in 89% yield. In addition, reduction of 2b with
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: ynishiha@okayama-u.ac.jp.
ORCID
Yasushi Nishihara: 0000-0001-5409-4207
Notes
Scheme 4. Transformation of Benzoisoselenazolone 2b
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was partly supported by ACT-C, JST, as well as a
Grant-in-Aid for Scientific Research (KAKENHI) (No.
16K17901) from JSPS. The Wesco Scientific Promotion
Foundation and the Japan Prize Foundation are acknowledged
for financial support. We gratefully thank Ms. Megumi Kosaka
and Mr. Motonari Kobayashi (Department of Instrumental
Analysis, Advanced Science Research Center, Okayama Uni-
versity) for performing elemental analyses and the SC-NMR
Laboratory (Okayama University) for the NMR spectral
measurements.
REFERENCES
■
(1) For reviews, see: (a) Mugesh, G.; du Mont, W.-W.; Sies, H. Chem.
Rev. 2001, 101, 2125. (b) Nogueira, C. W.; Zeni, G.; Rocha, J. B. T.
Chem. Rev. 2004, 104, 6255. (c) Bhabak, K. P.; Mugesh, G. Acc. Chem.
Res. 2010, 43, 1408. (d) Alberto, E. E.; do Nascimento, V.; Braga, A. L. J.
Braz. Chem. Soc. 2010, 21, 2032. (e) Orian, L.; Toppo, S. Free Radical
C
DOI: 10.1021/acs.orglett.7b00116
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Biol. Med. 2014, 66, 65. (f) Bhowmick, D.; Mugesh, G. Org. Biomol.
Chem. 2015, 13, 10262.
(i) Gao, F.; Zhu, W.; Zhang, D.; Li, S.; Wang, J.; Liu, H. J. Org. Chem.
2016, 81, 9122.
(2) (a) Bender, K. O.; Garland, M.; Ferreyra, J. A.; Hryckowian, A. J.;
Child, M. A.; Puri, A. W.; Solow-Cordero, D. E.; Higginbottom, S. K.;
Segal, E.; Banaei, N.; Shen, A.; Sonnenburg, J. L.; Bogyo, M. Sci. Transl.
Med. 2015, 7, No. 306ra148. (b) Wirth, T. Angew. Chem., Int. Ed. 2015,
54, 10074.
(3) Singh, N.; Halliday, A. C.; Thomas, J. M.; Kuznetsova, O. V.;
Baldwin, R.; Woon, E. C. Y.; Aley, P. K.; Antoniadou, I.; Sharp, T.;
Vasudevan, S. R.; Churchill, G. C. Nat. Commun. 2013, 4, 1332.
(4) For reviews, see: (a) Młochowski, J.; Brząszcz, M.; Giurg, M.; Palus,
(16) For related copper-mediated direct thiolation and selenation of
C(sp2)−H bonds, see: (a) Chen, X.; Hao, X.-S.; Goodhue, C. E.; Yu, J.-
Q. J. Am. Chem. Soc. 2006, 128, 6790. (b) Chu, L.; Yue, X.; Qing, F.-L.
Org. Lett. 2010, 12, 1644. (c) Tran, L. D.; Popov, I.; Daugulis, O. J. Am.
Chem. Soc. 2012, 134, 18237. (d) Sharma, P.; Rohilla, S.; Jain, N. J. Org.
Chem. 2015, 80, 4116. (e) Zhu, L.; Cao, X.; Qiu, R.; Iwasaki, T.; Reddy,
V. P.; Xu, X.; Yin, S.-F.; Kambe, N. RSC Adv. 2015, 5, 39358. For
rhodium-catalyzed reactions, see: (f) Yang, Y.; Hou, W.; Qin, L.; Du, J.;
Feng, H.; Zhou, B.; Li, Y. Chem. - Eur. J. 2014, 20, 416. (g) Wen, J.; Wu,
A.; Wang, M.; Zhu, J. J. Org. Chem. 2015, 80, 10457. (h) Xie, W.; Li, B.;
Wang, B. J. Org. Chem. 2016, 81, 396. (i) Yu, S.; Wan, B.; Li, X. Org. Lett.
2015, 17, 58. For palladium-catalyzed reactions, see: (j) Xu, C.; Shen, Q.
Org. Lett. 2014, 16, 2046. (k) Qiu, R.; Reddy, V. P.; Iwasaki, T.; Kambe,
N. J. Org. Chem. 2015, 80, 367. (l) Zhang, X.-S.; Li, G.; Zhang, X.-G.;
Zhang, X.-H. Tetrahedron 2015, 71, 5458. (m) Jin, W.; Zheng, P.; Law,
G.-L.; Wong, W.-T J. Organomet. Chem. 2016, 812, 66. For copper-
catalyzed reaction, see: (n) Yan, X.-B.; Gao, P.; Yang, H.-B.; Li, Y.-X.;
Liu, X.-Y.; Liang, Y.-M. Tetrahedron 2014, 70, 8730. (o) Mandal, A.;
Sahoo, H.; Baidya, M. Org. Lett. 2016, 18, 3202. (p) Liu, Y.; Huang, M.;
Wei, L. Asian J. Org. Chem. 2017, 6, 41. For cobalt-catalyzed reaction,
see: (q) Gensch, T.; Klauck, F. J. K.; Glorius, F. Angew. Chem., Int. Ed.
2016, 55, 11287. For ruthenium-catalyzed reaction, see: (r) Shu, S.;
Fan, Z.; Yao, Q.; Zhang, A. J. Org. Chem. 2016, 81, 5263.
J.; Woj
Santoro, S.; Shahzad, S. A.; Santi, C.; Wirth, T. Angew. Chem., Int. Ed.
2009, 48, 8409. (c) Młochowski, J.; Wojtowicz-Młochowska, H.
Molecules 2015, 20, 10205.
́
towicz, H. Eur. J. Org. Chem. 2003, 4329. (b) Freudendahl, D. M.;
́
(5) (a) Engman, L.; Hallberg, A. J. Org. Chem. 1989, 54, 2964.
(b) Oppenheimer, J.; Silks, L. A., III J. Labelled Compd. Radiopharm.
1996, 38, 281. (c) Chang, T.-C.; Huang, M.-L.; Hsu, W.-L.; Hwang, J.-
M.; Hsu, L.-Y. Chem. Pharm. Bull. 2003, 51, 1413. (d) Zade, S. S.; Panda,
S.; Singh, H. B.; Wolmershauser, G. Tetrahedron Lett. 2005, 46, 665.
̈
(6) (a) Lesser, R.; Weiß, R. Ber. Dtsch. Chem. Ges. B 1924, 57, 1077.
(b) Lambert, C.; Christiaens, L. Tetrahedron 1991, 47, 9053.
(c) Młochowski, J.; Kloc, K.; Syper, L.; Inglot, A. D.; Piasecki, E.
Liebigs. Ann. Chem. 1993, 1239. (d) Młochowski, J.; Gryglewski, R. J.;
Inglot, A. D.; Jakubowski, A.; Juchniewicz, L.; Kloc, K. Liebigs. Ann.
Chem. 1996, 1751. (e) Osajda, M.; Młochowski, J. Tetrahedron 2002, 58,
(17) Chen, F.-J.; Liao, G.; Li, X.; Wu, J.; Shi, B.-F. Org. Lett. 2014, 16,
5644.
́
7531. (f) Piętka-Ottlik, M.; Wojtowicz-Młochowska, H.; Kołodziejczyk,
(18) Crystallographic data for 2i have been deposited with the
Cambridge Crystallographic Data Centre as deposition no. CCDC-
1519835. This data can be obtained free of charge from the CCDC, 12
Union Road, Cambridge CB2 1EZ, UK [fax: + 44 (0)1223 336033 or
www.ccdc.cam.ac.uk/data_request/cif.
(19) For selected examples, see: (a) Fahey, D. R. J. Organomet. Chem.
1971, 27, 283. (b) Dick, A. R.; Hull, K. L.; Sanford, M. S. J. Am. Chem.
Soc. 2004, 126, 2300. (c) Wan, X.; Ma, Z.; Li, B.; Zhang, K.; Cao, S.;
Zhang, S.; Shi, Z. J. Am. Chem. Soc. 2006, 128, 7416. (d) Sun, X.; Shan,
K.; Piasecki, E.; Młochowski, J. Chem. Pharm. Bull. 2008, 56, 1423.
(7) (a) Fong, M. C.; Schiesser, C. H. Tetrahedron Lett. 1995, 36, 7329.
(b) Fong, M. C.; Schiesser, C. H. J. Org. Chem. 1997, 62, 3103.
(8) For other synthetic methods of benzoisoselenazolones, see:
(a) Zade, S. S.; Panda, S.; Tripathi, S. K.; Singh, H. B.; Wolmershauser,
̈
G. Eur. J. Org. Chem. 2004, 3857. (b) Sarma, B. K.; Mugesh, G. Chem. -
Eur. J. 2008, 14, 10603.
(9) (a) Balkrishna, S. J.; Bhakuni, B. S.; Chopra, D.; Kumar, S. Org. Lett.
2010, 12, 5394. (b) Balkrishna, S. J.; Bhakuni, B. S.; Kumar, S.
Tetrahedron 2011, 67, 9565.
(10) For recent reviews, see: (a) Satoh, T.; Miura, M. Chem. - Eur. J.
2010, 16, 11212. (b) Song, G.; Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41,
3651. (c) Zhu, C.; Wang, R.; Falck, J. R. Chem. - Asian J. 2012, 7, 1502.
(d) Gabriele, B.; Mancuso, R.; Salerno, G. Eur. J. Org. Chem. 2012, 6825.
(e) Ackermann, L. Acc. Chem. Res. 2014, 47, 281. (f) Zhu, R.-Y.; Farmer,
M. E.; Chen, Y.-Q.; Yu, J.-Q. Angew. Chem., Int. Ed. 2016, 55, 10578.
́
G.; Sun, Y.; Rao, Y. Angew. Chem., Int. Ed. 2013, 52, 4440. (e) Peron, F.;
Fossey, C.; Sopkova-de Oliveira Santos, J.; Cailly, T.; Fabis, F. Chem. -
Eur. J. 2014, 20, 7507. (f) Li, B.; Liu, B.; Shi, B.-F. Chem. Commun. 2015,
51, 5093. For a review, see: (g) Petrone, D. A.; Ye, J.; Lautens, M. Chem.
Rev. 2016, 116, 8003.
(20) See the Supporting Information for details.
(21) Uemura, T.; Yamaguchi, M.; Chatani, N. Angew. Chem., Int. Ed.
2016, 55, 3162.
(22) Simmons, E. M.; Hartwig, J. F. Angew. Chem., Int. Ed. 2012, 51,
3066.
(23) For single-electron oxidation of five-membered azanickelacycles,
see: (a) Ceder, R. M.; Granell, J.; Muller, G. Organometallics 1996, 15,
4618. (b) Higgs, A. T.; Zinn, P. J.; Simmons, S. J.; Sanford, M. S.
(g) Gulías, M.; Mascarenas, J. L. Angew. Chem., Int. Ed. 2016, 55, 11000.
̃
(11) For reviews, see: (a) Corbet, M.; De Campo, F. Angew. Chem., Int.
Ed. 2013, 52, 9896. (b) Rouquet, G.; Chatani, N. Angew. Chem., Int. Ed.
2013, 52, 11726. (c) Castro, L. C. M.; Chatani, N. Chem. Lett. 2015, 44,
410.
(12) Han, R.; Hillhouse, G. L. J. Am. Chem. Soc. 1998, 120, 7657.
(13) (a) Iwasaki, M.; Iyanaga, M.; Tsuchiya, Y.; Nishimura, Y.; Li, W.;
Li, Z.; Nishihara, Y. Chem. - Eur. J. 2014, 20, 2459. (b) Iwasaki, M.;
Tsuchiya, Y.; Nakajima, K.; Nishihara, Y. Org. Lett. 2014, 16, 4920.
(c) Iwasaki, M.; Kaneshika, W.; Tsuchiya, Y.; Nakajima, K.; Nishihara, Y.
J. Org. Chem. 2014, 79, 11330.
(14) For reviews, see: (a) Arisawa, M. Tetrahedron Lett. 2014, 55, 3391.
(b) Shen, C.; Zhang, P.; Sun, Q.; Bai, S.; Hor, T. S. A.; Liu, X. Chem. Soc.
Rev. 2015, 44, 291. (c) Iwasaki, M.; Nishihara, Y. Dalton Trans. 2016, 45,
15278.
(15) For related nickel-catalyzed direct formation of C−S and C−Se
bonds with the cleavage of C−H bonds, see: (a) Yang, K.; Wang, Y.;
Chen, X.; Kadi, A. A.; Fun, H.-K.; Sun, H.; Zhang, Y.; Lu, H. Chem.
Commun. 2015, 51, 3582. (b) Yan, S.-Y.; Liu, Y.-J.; Liu, B.; Liu, Y.-H.;
Shi, B.-F. Chem. Commun. 2015, 51, 4069. (c) Lin, C.; Li, D.; Wang, B.;
Yao, J.; Zhang, Y. Org. Lett. 2015, 17, 1328. (d) Wang, X.; Qiu, R.; Yan,
C.; Reddy, V. P.; Zhu, L.; Xu, X.; Yin, S.-F. Org. Lett. 2015, 17, 1970.
(e) Yokota, A.; Chatani, N. Chem. Lett. 2015, 44, 902. (f) Reddy, V. P.;
Qiu, R.; Iwasaki, T.; Kambe, N. Org. Biomol. Chem. 2015, 13, 6803.
(g) Peng, P.; Wang, J.; Li, C.; Zhu, W.; Jiang, H.; Liu, H. RSC Adv. 2016,
́
Organometallics 2009, 28, 6142. (c) Renz, A. L.; Perez, L. M.; Hall, M. B.
Organometallics 2011, 30, 6365. (d) Wu, X.; Zhao, Y.; Ge, H. J. Am.
Chem. Soc. 2014, 136, 1789. (e) Wu, X.; Zhao, Y.; Ge, H. Chem. - Eur. J.
2014, 20, 9530. (f) Aihara, Y.; Tobisu, M.; Fukumoto, Y.; Chatani, N. J.
Am. Chem. Soc. 2014, 136, 15509. (g) Yokota, A.; Chatani, N. Chem. Lett.
2015, 44, 902. (h) Yan, Q.; Chen, Z.; Yu, W.; Yin, H.; Liu, Z.; Zhang, Y.
Org. Lett. 2015, 17, 2482. (i) Xu, Z.-Y.; Jiang, Y.-Y.; Yu, H.-Z.; Fu, Y.
Chem. - Asian J. 2015, 10, 2479. (j) Kubo, T.; Chatani, N. Org. Lett. 2016,
18, 1698. (k) Aihara, Y.; Chatani, N. ACS Catal. 2016, 6, 4323.
(24) The possible formation of nickel(IV) species cannot be ruled out
because the addition of a radical scavenger, TEMPO (2,2,6,6-
tetramethylpiperidine 1-oxyl), did not suppress the reaction. We
supposed that TEMPO might also act as the single-electron oxidant
for the stable nickelacycle(II) species.
(25) Balkrishna, S. J.; Prasad, C. D.; Panini, P.; Detty, M. R.; Chopra,
D.; Kumar, S. J. Org. Chem. 2012, 77, 9541.
6, 57441. (h) Muller, T.; Ackermann, L. Chem. - Eur. J. 2016, 22, 14151.
̈
D
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