Oxidative Dehydrogenative [3+3] Annulation
Chin. J. Chem.
demonstrated by a gram scale reaction without diminished yield.
Further studies on developing more type of oxidative dehydro-
genative cyclization reactions to the synthesis of cyclic compounds
are currently underway.
tive Coupling and Oxidative-Amination Reactions of Ethers and Al-
cohols with Aromatics and Heteroaromatics. Chem. Sci. 2017, 8,
5845–5888; (d) Guo, S.-r.; Kumar, P. S.; Yang, M. Recent Advances of
Oxidative Radical Cross-Coupling Reactions: Direct α-C(sp3)-H Bond
Functionalization of Ethers and Alcohols. Adv. Synth. Catal. 2017, 359,
2–25; (e) Yi, H.; Zhang, G.; Wang, H.; Huang, Z.; Wang, J.; Singh, A. K.;
Lei, A. Recent Advances in Radical C–H Activation/Radical Cross-
Coupling. Chem. Rev. 2017, 117, 9016–9085; (f) Liu, C.; Yuan, J.; Gao,
M.; Tang, S.; Li, W.; Shi, R.; Lei, A. Oxidative Coupling between Two
Hydrocarbons: An Update of Recent C–H Functionalizations. Chem.
Rev. 2015, 115, 12138–12204; (g) Narayan, R.; Matcha, K.;
Antonchick, A. P. Metal-Free Oxidative C-C Bond Formation through
C-H Bond Functionalization. Chem. Eur. J. 2015, 21, 14678–14693; (h)
Hu, X.-Q.; Chen, J.-R.; Xiao, W.-J. Controllable Remote C-H Bond
Functionalization by Visible-Light Photocatalysis. Angew. Chem. Int.
Ed. 2017, 56, 1960–1962; (i) Qin, Y.; Zhu, L.; Luo, S. Organocatalysis
in Inert C–H Bond Functionalization. Chem. Rev. 2017, 117, 9433–
9520; (j) Ping, L.; Chung, D. S.; Bouffard, J.; Lee, S.-g. Transition Met-
al-Catalyzed Site- and Regio-Divergent C-H Bond Bunctionalization.
Chem. Soc. Rev. 2017, 46, 4299–4328.
Experimental
To a 10 mL reaction tube with a magnetic stirring bar were
added CH2Cl2 (3 mL), benzylhydrazines (1, 0.5 mmol) and Cu(OAc)2
(0.05 mmol) successively. The resulting reaction mixture was per-
formed at room temperature under oxygen atmosphere (balloon)
for 1 h. 3 Å molecular sieve was added for another 1 h. Aziridines
(2, 1 mmol) and BF3·Et2O (0.1 mmol) were then added. The solu-
tion was stirred at room temperature and completed within 3—10
h as monitored by TLC. The compounds B were isolated by column
chromatographic separation (hexane/DCM/EA = 5 : 3 : 0.2 to 5 : 3 :
0.6). Then to a 10 mL reaction tube with a magnetic stirring bar
were added above isolated compounds B, (CH2Cl)2 (1 mL),
PhI(OAc)2 (2 equiv.) and Zn(OTf)2 (10 mol%) successively. The re-
sulting reaction mixture was performed at 60 oC for 2—8 h as
monitored by TLC. After the reaction was completed, the reaction
mixture was concentrated under reduced pressure, and the resi-
due was purified by column chromatography to afford desired
products 3 (EA/hexane = 1 : 6 to 1 : 2).
[4] (a) Mei, R.; Sauermann, N.; Oliveira, J. C. A.; Ackermann, L. Electro-
removable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxida-
tive C–H/N–H Activation with Internal Alkynes. J. Am. Chem. Soc.
2018, 140, 7913–7921; (b) Li, J.; Huang, W.; Chen, J.; He, L.; Cheng, X.;
Li, G. Electrochemical Aziridination by Alkene Activation Using a Sul-
famate as the Nitrogen Source. Angew. Chem. Int. Ed. 2018, 57,
5695–5698; (c) Nguyen, T. T.; Grigorjeva, L.; Daugulis, O. Cobalt-Cat-
alyzed Coupling of Benzoic Acid C-H Bonds with Alkynes, Styrenes,
and 1,3-Dienes. Angew. Chem. Int. Ed. 2018, 57, 1688–1691; (d) Hou,
Z.-W.; Mao, Z.-Y.; Melcamu, Y. Y.; Lu, X.; Xu, H.-C. Electrochemical
Synthesis of Imidazo-Fused N-Heteroaromatic Compounds through a
C-N Bond-Forming Radical Cascade. Angew. Chem. Int. Ed. 2018, 57,
1636–1639; (e) Pan, J.; Li, X.; Qiu, X.; Luo, X.; Jiao, N. Copper-Cata-
lyzed Oxygenation Approach to Oxazoles from Amines, Alkynes, and
Molecular Oxygen. Org. Lett. 2018, 20, 2762–2765; (f) Li, H.; Huang,
S.; Wang, Y.; Huo, C. Oxidative Dehydrogenative [2 + 3]-Cyclization of
Glycine Esters with Aziridines Leading to Imidazolidines. Org. Lett.
2018, 20, 92–95; (g) Yi, H.; Niu, L.; Song, C.; Li, Y.; Dou, B.; Singh, A. K.;
Lei, A. Photocatalytic Dehydrogenative Cross-Coupling of Alkenes
with Alcohols or Azoles without External Oxidant. Angew. Chem. Int.
Ed. 2017, 56, 1120–1124; (h) Liu, K.; Tang, S.; Huang, P.; Lei, A. Ex-
ternal Oxidant-free Electrooxidative [3+2] Annulation between Phe-
nol and Indole Derivatives. Nat. Commun. 2017, 8, 775; (i) Xie, Z.; Jia,
J.; Liu, X.; Liu, L. Copper(II) Triflate-Catalyzed Aerobic Oxidative C-H
Functionalization of Glycine Derivatives with Olefins and Organobo-
ranes. Adv. Synth. Catal. 2016, 358, 919–925; (j) Xie, Z.; Liu, X.; Liu, L.
Copper-Catalyzed Aerobic Enantioselective Cross-Dehydrogenative
Coupling of N-Aryl Glycine Esters with Terminal Alkynes. Org. Lett.
2016, 18, 2982–2985; (k) Zhang, G.; Liu, C.; Yi, H.; Meng, Q.; Bian, C.;
Chen, H.; Jian, J.-X.; Wu, L.-Z.; Lei, A. External Oxidant-Free Oxidative
Cross-Coupling: A Photoredox Cobalt-Catalyzed Aromatic C–H Thiola-
tion for Constructing C–S Bonds. J. Am. Chem. Soc. 2015, 137, 9273–
9280; (l) Manna, S.; Antonchick, A. P. Copper-Catalyzed (2+1) Annu-
lation of Acetophenones with Maleimides: Direct Synthesis of Cyclo-
propanes. Angew. Chem. Int. Ed. 2015, 54, 14845–14848; (m) Huo, C.;
Yuan, Y.; Wu, M.; Jia, X.; Wang, X.; Chen, F.; Tang, J. Auto-Oxidative
Coupling of Glycine Derivatives. Angew. Chem. Int. Ed. 2014, 53,
13544–14547.
Supporting Information
The supporting information for this article is available on the
Acknowledgement
We thank the National Natural Science Foundation of China
(No. 21562037) for financially supporting this work.
References
[1] (a) Wurster, C.; Sendtner, R. Zur Kenntniss des Dimethylpara-
phenylendiamins. Chem. Ber. 1879, 12, 1803–1807; (b) Weitz, E.;
Schwechten, H. W. Über den Ammonium‐Charakter der Triarylamine.
(VII. Mitteilung über freie Ammonium‐Radikale.). Chem. Ber. 1926,
59, 2307; (c) Bauld, N. L.; Bellville, D. J.; Harirchian, B.; Lorenz, K. T.;
Pabon Jr, R. A.; Reynolds, D. W.; Wirth, D. D.; Chiou, H. S.; Marsh, B.
K. Cation Radical Pericyclic Reactions. Acc. Chem. Res. 1987, 20, 371–
378; (d) Bauld, N. L. Cation Radical Cycloadditions and Related Sig-
matropic Reactions. Tetrahedron 1989, 45, 5307–5363; (e) Popielarz,
R.; Arnold, D. R. Radical Ions in Photochemistry. Carbon-Carbon Bond
Cleavage of Radical Cations in Solution: Theory and Application. J.
Am. Chem. Soc. 1990, 112, 3068–3082; (f) Schmittle, M.; Burghart, A.
Understanding Reactivity Patterns of Radical Cations. Angew. Chem.
Int. Ed. 1997, 36, 2550–2589; (g) Zhang, C.; Tang, C.; Jiao, N. Recent
Advances in Copper-Catalyzed Dehydrogenative Functionalization via
a Single Electron Transfer (SET) Process. Chem. Soc. Rev. 2012, 41,
3464–3484; (h) Gini, A.; Brandhofer, T.; Mancheño, O. G. Recent
Progress in Mild Csp3–H Bond Dehydrogenative or (mono-) Oxidative
Functionalization. Org. Biomol. Chem. 2017, 15, 1294–1312; (i)
Beatty, J. W.; Stephenson, C. R. J. Amine Functionalization via Oxida-
tive Photoredox Catalysis: Methodology Development and Complex
Molecule Synthesis. Acc. Chem. Res. 2015, 48, 1474–1484.
[5] (a) Khoshneviszadeh, M.; Ghahremani, M. H.; Foroumadi, A.; Miri, R.;
Firuzi, O.; Madadkar-Sobhani, A.; Edraki, N.; Parsa, M.; Shafiee, A.
Design, Synthesis and Biological Evaluation of Novel Anti-Cytokine
1,2,4-Triazine Derivatives. Bioorg. Med. Chem. 2013, 21, 6708–6717;
(b) Karczmarzyk, Z.; Wysocki, W.; Urbaoczyk-Lipkowska, Z.; Kalicki, P.;
Bielawska, A.; Bielawski, K.; Ławecka, J. Synthetic Approaches for
Sulfur Derivatives Containing 1,2,4-Triazine Moiety: Their Activity for
in vitro Screening towards Two Human Cancer Cell Lines. J. Chem.
Pharm. Bull. 2015, 63, 531–537; (c) Sztanke, K.; Pasternak, K.; Rajtar,
[2] Huynh, M. H. V.; Meyer, T. J. Proton-Coupled Electron Transfer.
Chem. Rev. 2007, 107, 5004–5064.
[3] (a) Girard, S. A.; Knauber, T.; Li, C.-J. The Cross-Dehydrogenative
Coupling of C sp3-H Bonds: A Versatile Strategy for C-C Bond For-
mations. Angew. Chem. Int. Ed. 2014, 53, 74–100; (b) Murahashi, S.-I.;
Zhang, D. Ruthenium Catalyzed Biomimetic Oxidation in Organic
Synthesis Inspired by Cytochrome P-450. Chem. Soc. Rev. 2008, 37,
1490–1501; (c) Lakshman, M. K.; Vurama, P. K. Cross-Dehydrogena-
Chin. J. Chem. 2019, 37, 878-882
© 2019 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
881