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ChemComm
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COMMUNICATION
Journal Name
Chem. Commun., 2017, 53, 3399-3411; (d) Á. Vivancos, M.
DOI: 10.1039/C9CC00972H
Yao,, N. Lin, X-C. Qiao, J-W. Zhu and W. Deng,
some control in situ NMR experiments, which suggested a
bifunctional pendant base-assisted heterolytic H2 activation to
generate iridium hydride and an adjacent protic O–H
functionality for facile H+/H− transfer to the substrate
quinoxalines during hydrogenation. Presence of base
modulated the mechanism and plausibly did not allow the
ready availability of any protic O–H or proton to be transferred
to quinoxaline, which itself was a bad substrate for accepting
hydride from Ir–H. Interestingly, subsequent acid addition
reverses the situation and triggered hydrogenation by
protonating the neutral quinoxaline molecule to make it now
susceptible for hydride transfer from Ir–H generated from H2.
These results exemplified the possibility of devising new
switchable hydrogenation catalysis protocol by intercepting
the mechanistic paths with a harmonious combination of
suitable stimuli and appropriately designed catalyst. As the
present catalyst was also found to be effective in
dehydrogenation of the tetrahydroquinoxaline products (ESI),
switchable and reversible dehydrogenation/hydrogenation
catalysis would be the subject of future study.
Organometallics, 2018, 37, 3883−3892; (f) J. Wu, J. H.
Barnard, Y. Zhang, D. Talwar, C. M. Robertson and J. Xiao,
Chem. Commun., 2013, 49, 7052-7054; (g) H. Zhou, Z. Li, Z.
Wang, T. Wang, L. Xu, Y. He, Q-H. Fan, J. Pan, L. Gu and A. S.
C. Chan, Angew. Chem. Int. Ed., 2008, 47, 8464 –8467.
(a) P. Preuster, C. Papp and P. Wasserscheid, Acc. Chem.
Res., 2017, 50, 74−85; (b) M. Markiewicz, Y-Q. Zhang, M. T.
Empl, M. Lykaki, J. Tho¨ming, P. Steinberg and S. Stolte,
Energy Environ. Sci., 2019, 12, 366--383; (c) R. H. Crabtree,
ACS Sustainable Chem. Eng., 2017, 5, 4491−4498; (d) K.
Müller, K. Brooks and T. Autrey, Energy Fuels, 2018, 32,
10008−10015.
(a) M. Yamada and I. Honma, ChemPhysChem, 2004, 5, 724-
728; (b) C. S. Peng and A. Tokmakoff, J. Phys. Chem. Lett.,
2012, 3, 3302−3306; (c) Y. Nakane, T. Takeda, N. Hoshino, K.
Sakai and T. Akutagawa, J. Phys. Chem. A, 2015, 119,
6223−6231; (d) C. S. Peng, C. R. Baiz and A. Tokmakoff, Proc.
Natl. Acad. Sci. U.S.A., 2013, 110, 9243-9248; (e) J. Zhang, N.
Pidlypnyi, M. Nieger, J. C. Namysloa and A. Schmidt, Org.
Biomol. Chem., 2014, 12, 2737–2744.
For selected reviews, see: (a) S. Kuwata and T. Ikariya, Chem.
Commun., 2014, 50, 14290—14300; (b) R. H. Morris, Acc.
Chem. Res., 2015, 48, 1494−1502; (c) J. R. Khusnutdinova and
D. Milstein, Angew. Chem. Int. Ed., 2015, 54, 12236–12273;
(d) L. V. A. Hale and N. K. Szymczak, ACS Catal., 2018, 8,
6446−6461.
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This research was generously funded by SERB-DST, Govt. of
India (grant no. EMR/2016/003002) and IISER Bhopal. B.M.
thanks UGC, Govt. of India for doctoral fellowship. We thank
Abhishek Kumar for his help.
S. Siek, D. B. Burks, D. L. Gerlach, G. Liang, J. M. Tesh, C. R.
Thompson, F. Qu, J. E. Shankwitz, R. M. Vasquez, N.
Chambers, G. J. Szulczewski, D. B. Grotjahn, C. E. Webster
and E. T. Papish, Organometallics, 2017, 36, 1091−1106.
Notes and references
1
For reviews, see: (a) J. Choudhury, Tetrahedron Lett., 2018,
59, 487–495; (b) J. Choudhury and S. Semwal, Synlett, 2018,
29, 141–147; (c) V. Blanco, D.A. Leigh and V. Marcos, Chem.
Soc. Rev., 2015, 44, 5341–5370; (d) B.M. Neilson and C.W.
Bielawski, ACS Catal., 2013, 3, 1874–1885; (e) A.J. Teator,
D.N. Lastovickova and C.W. Bielawski, Chem. Rev., 2016, 116,
1969–1992; (f) G. Romanazzi, L. Degennaro, P. Mastrorilli
and R. Luisi, ACS Catal., 2017, 7, 4100–4114; (g) A.J. Teator
and C.W.J. Bielawski, Polym. Sci. Part A Polym. Chem., 2017,
55, 2949–2960; (h) Z. Yu and S. Hecht, Chem. Commun.,
2016, 52, 6639–6653; (i) S.M. Guillaume, E. Kirillov, Y. Sarazin
and J.-F. Carpentier, Chem. Eur. J., 2015, 21, 7988–8003; (j) F.
Wang, X. Liu and I. Willner, Angew. Chem. Int. Ed., 2015, 54,
1098–1129; (k) M. Schmittel, Chem. Commun., 2015, 51,
14956–14968; (l) A.M. Lifschitz, M.S. Rosen, C.M. McGuirk
and C.A. Mirkin, J. Am. Chem. Soc., 2015, 137, 7252–7261;
(m) R. Göstl, A. Senf and S. Hecht, Chem. Soc. Rev., 2014, 43,
1982–1996; (n) F.A. Leibfarth, K.M. Mattson, B.P. Fors, H.A.
Collins, C.J. Hawker, Angew. Chem. Int. Ed., 2013, 52, 199–
210; (o) N. Kumagai and M. Shibasaki, Catal. Sci. Technol.,
2013, 3, 41-57. (p) R.S. Stoll and S. Hecht, Angew. Chem. Int.
Ed., 2010, 49, 5054–5075; (q) U. Lüning, Angew. Chem. Int.
Ed., 2012, 51, 8163–8165.
2
3
4
(a) C. Hu, R. Duan, S. Yang, X. Pang and X. Chen,
Macromolecules, 2018, 51, 4699−4704; (b) O. Coulembier, S.
Moins, R. Todd and P. Dubois, Macromolecules, 2014, 47,
486−491.
(a) S. Semwal and J. Choudhury, ACS Catal., 2016, 6, 2424–
2428; (b) S. Semwal and J. Choudhury, Angew. Chem. Int. Ed.,
2017, 56, 5556–5560; (c) S. Semwal, A. Kumar and J.
Choudhury, Catal. Sci. Technol., 2018, 8, 6137-6142.
For selected recent examples, see: (a) G. E. Dobereiner, A.
Nova, N. D. Schley, N. Hazari, S. J. Miller, O. Eisenstein and R.
H. Crabtree, J. Am. Chem. Soc., 2011, 133, 7547–7562; (b) K.
Fujita, Y. Tanaka, M. Kobayashi and R. Yamaguchi, J. Am.
Chem. Soc., 2014, 136, 4829−4832; (c) C. Wang and J. Xiao,
4 | J. Name., 2012, 00, 1-3
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