Generic placeholder image

Current Organocatalysis

Editor-in-Chief

ISSN (Print): 2213-3372
ISSN (Online): 2213-3380

Review Article

Organocatalytic Synthesis of Heterocycles: A Brief Overview Covering Recent Aspects

Author(s): Rajib Sarkar* and Chhanda Mukhopadhyay*

Volume 8, Issue 1, 2021

Published on: 29 October, 2020

Page: [93 - 108] Pages: 16

DOI: 10.2174/2213337207999201029234021

Price: $65

Abstract

The use of small organic molecules as organocatalysts in organic synthesis has been intensely studied over the past decade. In this emerging field, considerable studies have led to the introduction of various efficient organocatalyzed synthetic methods of carbon-carbon and carbon- heteroatom bond formations. The use of these organocatalysts also showed environmentally benign reaction conditions compared to the metal-catalyzed transformations. In this review, we paid special attention to the most recent organocatalytic protocols reported for the synthesis of heterocycles. The studies have been outlined, depending on the organocatalysts used as: (i) nitrogen-based molecules as organocatalyst, (ii) NHCs as organocatalyst, and (iii) phosphorus-based molecules as organocatalysts. The discussion intends to reveal the scope as well as the vitality of organocatalysis in the area of heterocycle synthesis.

Keywords: Organocatalysis, organocatalyst, heterocycles, carbon-carbon bond formation, carbon-heteroatom bond formation.

Graphical Abstract
[1]
(a) Chanda, T.; Zhaoa, J.C-G. Recent progress in organocatalytic asymmetric domino transformations. Adv. Synth. Catal., 2018, 360, 2-79.
(b) Gurubrahamam, R.; Nagaraju, K.; Chen, K. Organocatalytic synthesis of densely functionalized oxa-bridged 2,6-epoxybenzo[b][1,5]oxazocine heterocycles. Chem. Commun. (Camb.), 2018, 54(47), 6048-6051.
(c) Oliveira, V.G.; Cardoso, M.F.C.; Forezi, L.S.M. Organocatalysis: A Brief Overview on Its Evolution and Applications. Catalysts, 2018, 8, 605.
[http://dx.doi.org/10.1002/adsc.201701059] [http://dx.doi.org/10.1039/C8CC02565G] [PMID: 29799038] [http://dx.doi.org/10.3390/catal8120605]
[2]
(a) Pellissier, H. Recent Developments in Enantioselective Organocatalytic Michael Reactions in Aqueous Media. Curr. Org. Chem., 2018, 22, 323-344.
(b) Shaikh, I. R. Organocatalysis: Key Trends in Green Synthetic Chemistry, Challenges, Scope towards Heterogenization, and Importance from Research and Industrial Point of View. J. Catal., 2014, 1-35.
[http://dx.doi.org/10.2174/1385272821666170818160915] [http://dx.doi.org/10.1155/2014/402860]
[3]
(a) Evans, C.S.; Davis, L.O. Recent Advances in Organocatalyzed Domino C-C Bond-Forming Reactions. Molecules, 2017, 23(1), 33-46.
(b) Theodorou, A.; Kokotos, C.G. Green Organocatalytic Synthesis of Indolines and Pyrrolidines from Alkenes. Adv. Synth. Catal., 2017, 359, 1577-1581.
[http://dx.doi.org/10.3390/molecules23010033] [PMID: 29295474] [http://dx.doi.org/10.1002/adsc.201601262]
[4]
(a) Wang, X.; Wang, Y.; Song, J.; Wei, D. Insights into N-heterocyclic carbene and Lewis acid cooperatively 8 catalyzed oxidative [3+3] annulation reactions of α, β-unsaturated 9 aldehyde with 1,3-dicarbonyl compounds. Org. Chem. Front., 2020, 7, 1113-1121.
(b) Flanigan, D.M.; Romanov-Michailidis, F.; White, N.A.; Rovis, T. Organocatalytic Reactions Enabled by N-Heterocyclic Carbenes. Chem. Rev., 2015, 115(17), 9307-9387.
[http://dx.doi.org/10.1039/D0QO00091D] [http://dx.doi.org/10.1021/acs.chemrev.5b00060] [PMID: 25992594]
[5]
(a) Guo, H.; Fan, Y.C.; Sun, Z.; Wu, Y.; Kwon, O. Phosphine Organocatalysis. Chem. Rev., 2018, 118(20), 10049-10293.
(b) Methot, J.L.; Roush, W.R. Nucleophilic Phosphine Organocatalysis. Adv. Synth. Catal., 2004, 346, 1035-1050.
[http://dx.doi.org/10.1021/acs.chemrev.8b00081] [PMID: 30260217] [http://dx.doi.org/10.1002/adsc.200404087]
[6]
(a) Martín-Acosta, P.; Feresin, G.; Tapia, A.; Estévez-Braun, A. Microwave-Assisted Organocatalytic Intramolecular Knoevenagel/Hetero Diels-Alder Reaction with O-(Arylpropynyloxy)-Salicylaldehydes: Synthesis of Polycyclic Embelin Derivatives. J. Org. Chem., 2016, 81(20), 9738-9756.
(b) Peña, R.; Martín, P.; Feresin, G.E.; Tapia, A.; Machín, F.; Estévez-Braun, A. Domino Synthesis of Embelin Derivatives with Antibacterial Activity. J. Nat. Prod., 2016, 79(4), 970-977.
[http://dx.doi.org/10.1021/acs.joc.6b01818] [PMID: 27680299] [http://dx.doi.org/10.1021/acs.jnatprod.5b01038] [PMID: 26924672]
[7]
Zhi, Y.; Zhao, K.; Liu, Q.; Wang, A.; Enders, D. Asymmetric synthesis of functionalized trifluoromethyl-substituted pyrrolidines via an organocatalytic domino Michael/Mannich [3+2] cycloaddition. Chem. Commun. (Camb.), 2016, 52(97), 14011-14014.
[http://dx.doi.org/10.1039/C6CC08352H] [PMID: 27853768]
[8]
Tan, Y.; Feng, E-L.; Sun, Q-S.; Lin, H.; Sun, X.; Lin, G-Q.; Sun, X-W. Enantioselective synthesis of spirooxindole benzoquinolizines via organo-catalyzed cascade reactions. Org. Biomol. Chem., 2017, 15(4), 778-781.
[http://dx.doi.org/10.1039/C6OB02157C] [PMID: 27808321]
[9]
Osorio-planes, L.; Rodriguez-Escrich, C.; Pericás, M.A. Removing the superfluous: A supportedsquaramide catalyst with a minimalistic linker applied to the enantioselective flow synthesis of pyranonaphthoquinones. Catal. Sci. Technol., 2016, 6, 4686-4689.
[http://dx.doi.org/10.1039/C6CY00473C]
[10]
Hazra, G.; Maity, S.; Bhowmick, S.; Ghorai, P. Organocatalytic, enantioselective synthesis of benzoxaboroles via Wittig/oxa-Michael reaction Cascade of α-formyl boronic acids. Chem. Sci. (Camb.), 2017, 8(4), 3026-3030.
[http://dx.doi.org/10.1039/C6SC04522G] [PMID: 28451370]
[11]
Chen, N.; Zhu, L.; Gan, L.; Liu, Z.; Wang, R.; Cai, X.; Jiang, X. Asymmetric synthesis of bispiro-[-butyrolactone-pyrrolidin-4,4′-pyrazolone] scaffolds containing two quaternary spirocenters via an organocatalytic 1,3-dipolar cycloaddition. Eur. J. Org. Chem., 2018, 2018, 2939-2943.
[http://dx.doi.org/10.1002/ejoc.201800404]
[12]
Andrés, J.M.; Maestro, A.; Valle, M.; Pedrosa, R. Chiral Bifunctional Thioureas and Squaramides and Their Copolymers as Recoverable Organocatalysts. Stereoselective Synthesis of 2-Substituted 4-Amino-3-nitrobenzopyrans and 3-Functionalized 3,4-Diamino-4 H-Chromenes. J. Org. Chem., 2018, 83(10), 5546-5557.
[http://dx.doi.org/10.1021/acs.joc.8b00567] [PMID: 29701971]
[13]
Zhou, X-J.; Zhao, J-Q.; Chen, X-M.; Zhuo, J-R.; Zhang, Y-P.; Chen, Y.Z.; Zhang, X.M.; Xu, X.Y.; Yuan, W.C. Organocatalyzed Asymmetric Dearomative Aza-Michael/Michael Addition Cascade of 2-Nitrobenzofurans and 2-Nitrobenzothiophenes with 2-Aminochalcones. J. Org. Chem., 2019, 84(7), 4381-4391.
[http://dx.doi.org/10.1021/acs.joc.9b00401] [PMID: 30865449]
[14]
Takaishi, K.; Okuyama, T.; Kadosaki, S.; Uchiyama, M.; Ema, T. Hemisquaramide Tweezers as Organocatalysts: Synthesis of Cyclic Carbonates from Epoxides and CO2. Org. Lett., 2019, 21(5), 1397-1401.
[http://dx.doi.org/10.1021/acs.orglett.9b00117] [PMID: 30763097]
[15]
Ping, X-N.; Wei, P-S.; Zhu, X-Q.; Xie, J-W. Catalyst-Controlled Switch in Diastereoselectivities: Enantioselective Construction of Functionalized 3,4-Dihydro-2H-thiopyrano[2,3-b]quinolines with Three Contiguous Stereocenters. J. Org. Chem., 2017, 82(4), 2205-2210.
[http://dx.doi.org/10.1021/acs.joc.6b02688] [PMID: 28103439]
[16]
Hong, M.; Kim, Y.; Kim, H.; Cho, H.J.; Baik, M.H.; Kim, Y. Scorpionate catalysts for coupling CO2 and epoxides to cyclic carbonates: A rational design approach for organocatalysts. J. Org. Chem., 2018, 83(16), 9370-9380.
[http://dx.doi.org/10.1021/acs.joc.8b00722] [PMID: 29924610]
[17]
Kasar, S.B.; Thopate, S.R. Ultrasonically Assisted Efficient and Green Protocol for the Synthesis of 4H-isoxazol-5-ones using Itaconic Acid as a Homogeneous and Reusable Organocatalyst. Curr. Organocatal., 2019, 6, 231-237.
[http://dx.doi.org/10.2174/2213337206666190411115402]
[18]
Mondal, B.; Balha, M.; Pan, S.C. Organocatalytic asymmetric spirocyclization reactions of cyclic 2,4-dienones with cyanoketones: synthesis of spiro-dihydropyrano cyclohexanones. Org. Biomol. Chem., 2019, 17(34), 7849-7853.
[http://dx.doi.org/10.1039/C9OB01415B] [PMID: 31393510]
[19]
Bu, H-Z.; Li, H-H.; Luo, W-F.; Luo, C.; Qian, P-C.Ye.; Ye, L.W. Synthesis of 2H-Chromenes via Unexpected [4 + 2] Annulation of Alkynyl Thioethers with o-Hydroxybenzyl Alcohols. Org. Lett., 2020, 22(2), 648-652.
[http://dx.doi.org/10.1021/acs.orglett.9b04421] [PMID: 31887060]
[20]
Xie, Q.; Long, H-J.; Zhang, Q-Y.; Tang, P.; Deng, J. Enantioselective Syntheses of 4H-3,1-Benzoxazines via Catalytic Asymmetric Chlorocyclization of o-Vinylanilides. J. Org. Chem., 2020, 85(4), 1882-1893.
[http://dx.doi.org/10.1021/acs.joc.9b02395] [PMID: 31880445]
[21]
Janssen-Müller, D.; Singha, S.; Olyschläger, T.; Daniliuc, C.G.; Glorius, F. Annulation of o-Quinodimethanes through N-Heterocyclic Carbene Catalysis for the Synthesis of 1-Isochromanones. Org. Lett., 2016, 18(17), 4444-4447.
[http://dx.doi.org/10.1021/acs.orglett.6b02335] [PMID: 27549614]
[22]
Ema, T.; Nanjo, Y.; Shiratori, S.; Terao, Y.; Kimura, R. Solvent-Free Benzoin and Stetter Reactions with a Small Amount of NHC Catalyst in the Liquid or Semisolid State. Org. Lett., 2016, 18(21), 5764-5767.
[http://dx.doi.org/10.1021/acs.orglett.6b03115] [PMID: 27779419]
[23]
Wang, Y.; Oriez, R.; Kuwano, S.; Yamaoka, Y.; Takasu, K.; Yamada, K. Oxa- and Azacycle Formation via Migrative Cyclization of Sulfonylalkynol and Sulfonylalkynamide with N-Heterocyclic Carbene. J. Org. Chem., 2016, 81(6), 2652-2664.
[http://dx.doi.org/10.1021/acs.joc.6b00182] [PMID: 26930143]
[24]
Mondal, S.; Mukherjee, S.; Das, T.K.; Gonnade, R.G.; Biju, A.T. Enantioselective Synthesis of Functionalized β-Lactones by NHC- Catalyzed Aldol Lactonization of Ketoacids. J. Org. Chem., 2017, 82(17), 9223-9228.
[http://dx.doi.org/10.1021/acs.joc.7b01526] [PMID: 28774172]
[25]
Yan, J.; Song, Z.; Zhao, C.; Shi, K.; Yang, L.; Zhong, G. Highly Chemoselective and Enantioselective Synthesis of 3,4-2H-Pyrindin-2-ones by an NHC-Catalyzed [3 + 3] Cyclization. Org. Lett., 2020, 22(9), 3329-3334.
[http://dx.doi.org/10.1021/acs.orglett.0c00699] [PMID: 32157889]
[26]
Wang, B.; Huang, L.; Hou, Y.; Lan, S.; Cheng, J. N-Heterocyclic Carbene (NHC) Organocatalytic One-Pot Reaction for the Enantioselective Synthesis of Fluoromethylated Chromenones. Org. Lett., 2018, 20(19), 6012-6016.
[http://dx.doi.org/10.1021/acs.orglett.8b02300] [PMID: 30260653]
[27]
Fang, S.; Jin, S.; Ma, R.; Lu, T.; Du, D. Asymmetric Synthesis of C2-Quaternary Indolin-3-ones Enabled by N-Heterocyclic Carbene Catalysis. Org. Lett., 2019, 21(13), 5211-5214.
[http://dx.doi.org/10.1021/acs.orglett.9b01823] [PMID: 31247739]
[28]
He, C.; Li, Z.; Zhou, H.; Xu, J. Stereoselective [8 + 2] Cycloaddition Reaction of Azaheptafulvenes with α-Chloro Aldehydes via N-Heterocyclic Carbene Catalysis. Org. Lett., 2019, 21(19), 8022-8026.
[http://dx.doi.org/10.1021/acs.orglett.9b03014] [PMID: 31556301]
[29]
Li, T.; Wang, J.; Xu, J.; Jin, J.; Chi, Y.R.; Jin, Z. Enantio- and Diastereoselective Synthesis of Chromeno[4,3-b]pyrrole Derivatives Bearing Tetrasubstituted Chirality Centers through Carbene Catalyzed Cascade Reactions. Org. Lett., 2020, 22(1), 326-330.
[http://dx.doi.org/10.1021/acs.orglett.9b04371] [PMID: 31833772]
[30]
Wang, C.; Wang, Z.; Yang, J.; Shi, S-H.; Hui, X-P. Sequential Visible-Light and N-Heterocyclic Carbene Catalysis: Stereoselective Synthesis of Tetrahydropyrano[2,3-b]indoles. Org. Lett., 2020, 22(11), 4440-4443.
[http://dx.doi.org/10.1021/acs.orglett.0c01447] [PMID: 32380832]
[31]
Ni, H.; Yao, W.; Waheed, A.; Ullah, N.; Lu, Y. Enantioselective [4 + 2]-annulation of oxadienes and allenones catalyzed by an amino acid derived phosphine: Synthesis of functionalized dihydropyrans. Org. Lett., 2016, 18(9), 2138-2141.
[http://dx.doi.org/10.1021/acs.orglett.6b00760] [PMID: 27091405]
[32]
Sankar, M.G.; Garcia-Castro, M.; Golz, C.; Strohmann, C.; Kumar, K. Engaging allene-derived zwitterions in an unprecedented mode of asymmetric [3 + 2]-annulation reaction. Angew. Chem. Int. Ed. Engl., 2016, 55(33), 9709-9713.
[http://dx.doi.org/10.1002/anie.201603936] [PMID: 27345724]
[33]
Wang, D.; Tong, X. Phosphine-catalyzed asymmetric [3 + 2] annulations of δ-acetoxy allenoates with 2-naphthols. Org. Lett., 2017, 19(23), 6392-6395.
[http://dx.doi.org/10.1021/acs.orglett.7b03250] [PMID: 29152982]
[34]
Ni, C.; Chen, J.; Zhang, Y.; Hou, Y.; Wang, D.; Tong, X.; Zhu, S.F.; Zhou, Q.L. Phosphine-catalyzed asymmetric [3 + 2] annulations of δ-acetoxy allenoates with β-carbonyl amides: Enantioselective synthesis of spirocyclic β-keto γ-lactams. Org. Lett., 2017, 19(13), 3668-3671.
[http://dx.doi.org/10.1021/acs.orglett.7b01717] [PMID: 28656768]
[35]
Zhu, Y-J.; Guo, X-F.; Fan, Z-J.; Chen, L.; Ma, L-Y.; Wang, H-X.; Wei, Y.; Xu, X-M.; Lin, J-P.; Bakulev, V.A. Approach to thiazole-containing tetrahydropyridines via aza-Rauhut-Currier reaction and their potent fungicidal and insecticidal activity. RSC Advances, 2016, 6, 112704-112711.
[http://dx.doi.org/10.1039/C6RA24342H]
[36]
Xing, J.; Lei, Y.; Gao, Y.N.; Shi, M. PPh3-catalyzed [3 + 2] spiroannulation of 1C,3N-bisnucleophiles derived from secondary β-ketoamides with δ-acetoxy allenoate: A route to functionalized spiro N-heterocyclic derivatives. Org. Lett., 2017, 19(9), 2382-2385.
[http://dx.doi.org/10.1021/acs.orglett.7b00910] [PMID: 28443669]
[37]
Huang, Z.; Bao, Y.; Zhang, Y.; Yang, F.; Lu, T.; Zhou, Q. Hydroxy-assisted regio- and stereoselective synthesis of functionalized 4-methylenepyrrolidine derivatives via phosphine-catalyzed [3 + 2] cycloaddition of allenoates with o-hydroxyaryl azomethine ylides. J. Org. Chem., 2017, 82(23), 12726-12734.
[http://dx.doi.org/10.1021/acs.joc.7b02560] [PMID: 29125296]
[38]
Zielke, K.; Waser, M. Formal (4 + 1)-Addition of Allenoates to o-Quinone Methides. Org. Lett., 2018, 20(3), 768-771.
[http://dx.doi.org/10.1021/acs.orglett.7b03906] [PMID: 29350040]
[39]
Xu, C.; Wittmann, S.; Gemander, M.; Ruohonen, V.; Clark, J.S. Trialkylphosphine-Mediated Synthesis of 2-Acyl Furans from Ynenones. Org. Lett., 2017, 19(13), 3556-3559.
[http://dx.doi.org/10.1021/acs.orglett.7b01533] [PMID: 28654294]
[40]
Jin, H.; Zhang, Q.; Li, E.; Jia, P.; Li, N.; Huang, Y. Phosphine-catalyzed intramolecular Rauhut-Currier reaction: enantioselective synthesis of hydro-2H-indole derivatives. Org. Biomol. Chem., 2017, 15(34), 7097-7101.
[http://dx.doi.org/10.1039/C7OB01820G] [PMID: 28816332]
[41]
Zhang, X.Z.; Gan, K.J.; Liu, X.X.; Deng, Y.H.; Wang, F.X.; Yu, K.Y.; Zhang, J.; Fan, C.A. Enantioselective synthesis of functionalized 4-aryl hydrocoumarins and 4-aryl hydroquinolin-2-ones via intramolecular vinylogous Rauhut-Currier reaction of paraquinone methides. Org. Lett., 2017, 19(12), 3207-3210.
[http://dx.doi.org/10.1021/acs.orglett.7b01331] [PMID: 28581760]
[42]
Kondo, M.; Wathsala, H.D.P.; Sako, M.; Hanatani, Y.; Ishikawa, K.; Hara, S.; Takaai, T.; Washio, T.; Takizawa, S.; Sasai, H. Exploration of flow reaction conditions using machine-learning for enantioselective organocatalyzed Rauhut-Currier and [3+2] annulation sequence. Chem. Commun. (Camb.), 2020, 56(8), 1259-1262.
[http://dx.doi.org/10.1039/C9CC08526B] [PMID: 31903462]
[43]
Wang, H.; Zhou, W.; Tao, M.; Hu, A.; Zhang, J. Functionalized tetrahydropyridines by enantioselective phosphine-catalyzed aza-[4 +2] cycloaddition of N-sulfonyl-1-aza-1,3-dienes with vinyl ketones. Org. Lett., 2017, 19(7), 1710-1713.
[http://dx.doi.org/10.1021/acs.orglett.7b00489] [PMID: 28328230]
[44]
Yao, W.; Yu, Z.; Wen, S.; Ni, H.; Ullah, N.; Lan, Y.; Lu, Y. Chiral phosphine-mediated intramolecular [3 + 2] annulation: Enhanced enantioselectivity by achiral Brønsted acid. Chem. Sci. (Camb.), 2017, 8(7), 5196-5200.
[http://dx.doi.org/10.1039/C7SC00952F] [PMID: 28970906]
[45]
Del Corte, X.; Maestro, A.; Vicario, J.; Martinez de Marigorta, E.; Palacios, F. Brönsted-Acid-Catalyzed Asymmetric Three-Component Reaction of Amines, Aldehydes, and Pyruvate Derivatives. Enantioselective Synthesis of Highly Functionalized γ-Lactam Derivatives. Org. Lett., 2018, 20(2), 317-320.
[http://dx.doi.org/10.1021/acs.orglett.7b03397] [PMID: 29282981]
[46]
Xiong, W.; Li, S.; Fu, B.; Wang, J.; Wang, Q-A.; Yang, W. Visible-Light Induction/Brønsted Acid Catalysis in Relay for the Enantioselective Synthesis of Tetrahydroquinolines. Org. Lett., 2019, 21(11), 4173-4176.
[http://dx.doi.org/10.1021/acs.orglett.9b01354] [PMID: 31124682]
[47]
Shao, Y-D.; Dong, M-M.; Wang, Y-A.; Cheng, P-M.; Wang, T.; Cheng, D-J. Organocatalytic Atroposelective Friedländer Quinoline Heteroannulation. Org. Lett., 2019, 21(12), 4831-4836.
[http://dx.doi.org/10.1021/acs.orglett.9b01731] [PMID: 31180222]
[48]
Zhang, P.; Guo, X.; Liu, C.; Li, W.; Li, P. Enantioselective Construction of Pyridine N-Oxides Featuring 2,3-Dihydrofuran Motifs via Phosphine-Catalyzed [4 + 1]-Annulation of 2-Enoylpyridine N-Oxides with Morita-Baylis-Hillman Carbonates. Org. Lett., 2019, 21(1), 152-155.
[http://dx.doi.org/10.1021/acs.orglett.8b03612] [PMID: 30574783]

Rights & Permissions Print Export Cite as
© 2022 Bentham Science Publishers | Privacy Policy