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ACS Catalysis
Isocoumarins. J. Org. Chem. 2015, 80, 620–627. (b) Chu, H.; Sun,
Catalyzed Alkyne Annulation by Anilines: Versatile Indole
Synthesis by C–H/N–H Functionalization. Chem. Commun. 2013,
49, 6638–6640. (d) Ackermann, L.; Lygin, A. V. Cationic
Ruthenium(II) Catalysts for Oxidative C–H/N–H Bond
Functionalizations of Anilines with Removable Directing Group:
Synthesis of Indoles in Water. Org. Lett. 2012, 14, 764–767. (e)
Wang, H.; Grohmann, C.; Nimphius, C.; Glorius, F. Mild Rh(III)-
Catalyzed C–H Activation and Annulation with Alkyne MIDA
Boronates: Short, Efficient Synthesis of Heterocyclic Boronic Acid
Derivatives. J. Am. Chem. Soc. 2012, 134, 19592–19595. (f) Huestis,
M. P.; Chan, L.; Stuart, D. R.; Fagnou, K. The Vinyl Moiety as a
Handle for Regiocontrol in the Preparation of Unsymmetrical 2,3-
Aliphatic-Substituted Indoles and Pyrroles. Angew. Chem. Int. Ed.
2011, 50, 1338–1341. (g) Chen, J.; Pang, Q.; Sun, Y.; Li, X. Synthesis
of N-(2-Pyridyl)indoles via Pd(II)-Catalyzed Oxidative Coupling.
J. Org. Chem. 2011, 76, 3523–3526. (h) Zhou, F.; Han, X.; Lu, X.
Synthesis of Indoles via Palladium-Catalyzed C–H Activation of
N-Aryl Amides Followed by Coupling with Alkynes. Tetrahedron
Lett. 2011, 52, 4681–4685. (i) Stuart, D. R.; Alsabeh, P.; Kuhn, M.;
Fagnou, K. Rhodium(III)-Catalyzed Arene and Alkene C–H Bond
Functionalization Leading to Indoles and Pyrroles. J. Am. Chem.
Soc. 2010, 132, 18326–18339. (j) Stuart, D. R.; Bertrand-Laperle, M.;
Burgess, K. M. N.; Fagnou, K. Indole Synthesis via Rhodium
Catalyzed Oxidative Coupling of Acetanilides and Internal
Alkynes. J. Am. Chem. Soc. 2008, 130, 16474–16475.
S.; Yu, J.-T.; Cheng, J. Rh-Catalyzed Sequential Oxidative C–H
Activation/Annulation with Geminal-Substituted Vinyl Acetates
to Access Isoquinolines. Chem. Commun. 2015, 51, 13327–13329. (c)
Webb, N. J.; Marsden, S. P.; Raw, S. A. Rhodium(III)-Catalyzed
C−H Activation/Annulation with Vinyl Esters as an Acetylene
Equivalent. Org. Lett. 2014, 16, 4718–4721.
(7) Huang, J.-R.; Bolm, C. Microwave-Assisted Synthesis of
Heterocycles by Rhodium(III)-Catalyzed Annulation of N-
Methoxyamides with -Chloroaldehydes. Angew. Chem. Int. Ed.
2017, 56, 15921–15925.
(8) (a) Kim, K. H.; Park, B. R.; Lim, J. W.; Kim, J. N. An Efficient
Palladium-Catalyzed Synthesis of Benzils from Aryl Bromides:
Vinylene Carbonate as a Synthetic Equivalent of Glyoxal.
Tetrahedron Lett. 2011, 52, 3463–3466. (b) Hilf, S.; Grubbs, R. H.;
Kilbinger, A. F. M. End Capping Ring-Opening Olefin Metathesis
Polymerization Polymers with Vinyl Lactones. J. Am. Chem. Soc.
2008, 130, 11040–11048. (c) Samizu, K.; Ogasawara, K. Palladium-
Mediated Formation of N-Acyl-2-hydroxuindolines: A New Entry
into N-Acylindoles. Heterocycles 1995, 41, 1627–1629.
(9) Hara, H.; Hirano, M. Tanaka, K. A New Route to Substituted
Phenols by Cationic Rhodium(I)/BINAP Complex-Catalyzed
Decarboxylative [2+2+2] Cycloaddition. Org. Lett. 2009, 11, 1337–
1340.
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(10) Wang, Z.; Xue, F.; Hayashi, T. Synthesis of
Arylacetaldehydes by Iridium-Catalyzed Arylation of Vinylene
Carbonate with Arylboronic Acids. Angew. Chem. Int. Ed. 2019, 58,
11054–11057.
(17) Early examples for C–H/(imidazole, pyrrol)N–H oxidative
annulation (see the Supporting Information for all references): (a)
Kavitha, N.; Sukumar, G.; Kumar, V. P.; Mainkar, P. S.;
Chandrasekhar,
S.
Ruthenium-Catalyzed
(11) For a review, see: Huang, H.; Ji, X.; Wu, W.; Jiang, H.
Transition metal-catalyzed C–H functionalization of N-
oxyenamine internal oxidants. Chem. Soc. Rev. 2015, 44, 1155–1171.
(12) For seminal work, see: (a) Rakshit, S.; Grohmann, C.;
Besset, T.; Glorius, F. Rh(III)-Catalyzed Directed C–H Olefination
Using an Oxidizing Directing Group: Mild, Efficient, and
Versatile. J. Am. Chem. Soc. 2011, 133, 2350–2353. (b) Tan, Y.;
Hartwig, J. F. Palladium-Catalyzed Amination of Aromatic C–H
Bonds with Oxime Esters. J. Am. Chem. Soc. 2010, 132, 3676–3677.
(c) Ng, K.-H.; Chan, A. S. C.; Yu, W.-Y. Pd-Catalyzed
Intermolecular ortho-C–H Amidation of Anilides by N-
Nosyloxycarbamate. J. Am. Chem. Soc. 2010, 132, 12862–12864. (d)
Guimond, N.; Gouliaras, C.; Fagnou, K. Rhodium(III)-Catalyzed
Isoquinolone Synthesis: The N–O Bond as a Handle for C–N Bond
Formation and Catalyst Turnover. J. Am. Chem. Soc. 2010, 132,
6908–6909. (e) Wu, J.; Cui, X.; Chen, L.; Jiang, G.; Wu, Y.
Palladium-Catalyzed Alkenylation of Quinoline-N-oxides via C−H
Activation under External-Oxidant-Free Conditions. J. Am. Chem.
Soc. 2009, 131, 13888–13889.
Benzimidazoisoquinoline Synthesis via Oxidative Coupling of 2-
Arylbenzimidazoles with Alkynes. Tetrahedron Lett. 2013, 54,
4198–4201. (b) Ma, W.; Graczyk, K.; Ackermann, L. Ruthenium-
Catalyzed Alkyne Annulations with Substituted 1H-Pyrazoles by
C–H/N–H Bond Functionalizations. Org. Lett. 2012, 14, 6318–6321.
(c) Li, X.; Zhao, M. Rhodium(III)-Catalyzed Oxidative Coupling of
5-Aryl-1H-pyrazoles with Alkynes and Acrylates. J. Org. Chem.
2011, 76, 8530–8536. (d) Morimoto, K.; Hirano, K.; Satoh, T.;
Miura, M. Rhodium-Catalyzed Oxidative Coupling/Cyclization of
2-Phenylindoles with Alkynes via C–H and N–H Bond Cleavages
with Air as the Oxidant. Org. Lett. 2010, 12, 2068–2071. (e) Umeda,
N.; Tsurugi, H.; Satoh, T.; Miura, M. Fluorescent Naphthyl- and
Anthrylazoles from the Catalytic Coupling of Phenylazoles with
Internal Alkynes through the Cleavage of Multiple C–H Bonds.
Angew. Chem. Int. Ed. 2008, 47, 4019–4022.
(18) C–H/N–H Oxidative annulation for amide-based
heterocycles: (a) Lin, H.; Li, S.-S.; Dong, L. Synthesis of Indoles
and Polycyclic Amides via Ruthenium(II)-Catalyzed C–H
Activation and Annulation. Org. Biomol. Chem. 2015, 13, 11228–
11234. (b) Yu, B.; Chen, Y.; Hong, M.; Duan, P.; Gan, S.; Chao, H.;
Zhao, Z.; Zhao, J. Rhodium-Catalyzed C–H Activation of
Hydrazines Leads to Isoquinolones with Tunable Aggregation-
Induced Emission Properties. Chem. Commun. 2015, 51, 14365–
14368. (c) Su, B.; Wei, J.-B.; Wu, W.-L.; Shi, Z.-J. Diversity-
(13) Guimond, N.; Gorelsky, S. I. Fagnou, K. Rhodium(III)-
Catalyzed Heterocycle Synthesis Using an Internal Oxidant:
Improved Reactivity and Mechanistic Studies. J. Am. Chem. Soc.
2011, 133, 6449–6457.
(14) Nucleophilic attack of the nitrogen atom to the carbon
atom (6-exo-tet) might give the same intermediate C.
Oriented Synthesis
Transformations of
through
Novel Multirole Directing Group.
Rh-Catalyzed
Selective
(15) The CCDC numbers are 1955991 (7c), 1955992 (7e). These
data are available free of charge from The Cambridge
a
ChemCatChem 2015, 7, 2986–2990. (d) Li, B.; Feng, H.; Wang, N.;
Ma, J.; Song, H.; Xu, S.; Wang, B. Ruthenium-Catalyzed Oxidative
Coupling/Cyclization of Isoquinolones with Alkynes through C–
H/N–H Activation: Mechanism Study and Synthesis of
Dibenzo[a,g]quinolizin-8-one Derivatives. Chem. Eur. J. 2012, 18,
12873–12879. (e) Song, G.; Chen, D.; Pan, C.-L.; Crabtree, R. H.; Li,
X. Rh-Catalyzed Oxidative Coupling between Primary and
Secondary Benzamides and Alkynes: Synthesis of Polycyclic
Amides. J. Org. Chem. 2010, 75, 7487–7490.
Crystallographic
Data
Centre
via
(16) Early examples for indole synthesis via C–H/N–H oxidative
annulation (see the Supporting Information for all references): (a)
Hoshino, Y.; Shibata, Y.; Tanaka, K. Oxidative Annulation of
Anilides with Internal Alkynes Using an (Electron-Deficient η5-
Cyclopentadienyl)Rhodium(III)
Catalyst
under
Ambient
Conditions. Adv. Synth. Catal. 2014, 356, 1577–1585. (b)
Kathiravan, S.; Nicholls, I. A. Rhodium(III)-Catalysed Aerobic
Synthesis of Highly Functionalized Indoles from N-Arylurea
under Mild Conditions through C–H Activation. Chem. Commun.
2014, 50, 14964–14967. (c) Song, W.; Ackermann, L. Nickel-
(19) Early examples for C–H/(imine)N–H oxidative annulation
(see the Supporting Information for all references): (a) He, R.;
Huang, Z.-T.; Zheng, Q.-Y.; Wang, C. Manganese-Catalyzed
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