Phosphine-Catalyzed Divergent γ,γ- and ε,γ-Umpolung Domino Additions of Bisoxindoles with Allenoates: Construction of Vicinal All-Carbon Quaternary Stereocenters and Formal Total Synthesis of Dimeric Cyclotryptamine Alkaloids
Yufei Zhang
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Search for more papers by this authorJing Chen
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Search for more papers by this authorCorresponding Author
Hui Yao
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Hubei Three Gorges Laboratory, Yichang, Hubei, 443007 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorYuanbin Wang
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Search for more papers by this authorHongyu Liu
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Search for more papers by this authorLong Wang
College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang, Hubei, 443002 China
Search for more papers by this authorCorresponding Author
Nianyu Huang
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Hubei Three Gorges Laboratory, Yichang, Hubei, 443007 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorCorresponding Author
Nengzhong Wang
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Hubei Three Gorges Laboratory, Yichang, Hubei, 443007 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorYufei Zhang
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Search for more papers by this authorJing Chen
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Search for more papers by this authorCorresponding Author
Hui Yao
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Hubei Three Gorges Laboratory, Yichang, Hubei, 443007 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorYuanbin Wang
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Search for more papers by this authorHongyu Liu
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Search for more papers by this authorLong Wang
College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang, Hubei, 443002 China
Search for more papers by this authorCorresponding Author
Nianyu Huang
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Hubei Three Gorges Laboratory, Yichang, Hubei, 443007 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorCorresponding Author
Nengzhong Wang
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei, 443002 China
Hubei Three Gorges Laboratory, Yichang, Hubei, 443007 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorComprehensive Summary
Vicinal all-carbon quaternary stereocenters are widely present in natural products and bioactive molecules. However, the construction of such motif in one step from readily available starting materials remains a significant challenge. Herein, we report a phosphine-catalyzed divergent γ,γ- and ε,γ-umpolung domino addition of bisoxindoles with allenoates. This method serves as a practical tool for the concise synthesis of a series of bisoxindole derivatives bearing sterically hindered vicinal all-carbon quaternary stereocenters under mild reaction conditions. The applicability of this novel method was demonstrated with the gram-scale synthesis of three known advanced intermediates for the total syntheses of calycanthine, chimonanthine and folicanthine.
Supporting Information
| Filename | Description |
|---|---|
| cjoc202401240-sup-0001-Supinfo.pdfPDF document, 11.2 MB |
Appendix S1: Supporting Information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1 Eccles, R. G. Calycanthine. Drug. Circ. Chem. Gaz. 1888, 32, 65.
- 2(a) May, J. A.; Stoltz, B. The Structural and Synthetic Implications of the Biosynthesis of the Calycanthaceous Alkaloids, the Communesins, and Nomofungin. Tetrahedron 2006, 62, 5262−5271; (b) Schmidt, M. A.; Movassaghi, M. New Strategies for the Synthesis of Hexahydropyrroloindole Alkaloids Inspired by Biosynthetic Hypotheses. Synlett 2008, 2008, 313−324; (c) Steven, A.; Overman, L. E. Total Synthesis of Complex Cyclotryptamine Alkaloids: Stereocontrolled Construction of Quaternary Carbon Stereocenters. Angew. Chem. Int. Ed. 2007, 46, 5488−5508; (d) Trost, B. M.; Osipov, M. Recent Advances on the Total Synthesis of Communesin Alkaloids and Perophoramidine. Chem. - Eur. J. 2015, 21, 16318−16343; (e) Xu, J.-B.; Cheng, K.-J. Studies on the Alkaloids of the Calycanthaceae and Their Syntheses. Molecules 2015, 20, 6715−6738; (f) Ma, Z.; Zhou, A.; Xia, C. Strategies for Total Synthesis of Bispyrrolidino Alkaloids. Nat. Prod. Rep. 2022, 39, 1015−1044.
- 3(a) Link, J. T.; Overman, L. E. Stereocontrolled Total Syntheses of meso-Chimonanthine and meso-Calycanthine via a Novel Samarium Mediated Reductive Dialkylation. J. Am. Chem. Soc. 1996, 118, 8166–8167; (b) Movassaghi, M.; Schmidt, M. A. Concise Total Synthesis of (–)-Calycanthine, (+)-Chimonanthine, and (+)-Folicanthine. Angew. Chem. Int. Ed. 2007, 46, 3725–3728; (c) Mitsunuma, H.; Shibasaki, M.; Kanai, M.; Matsunaga, S. Catalytic Asymmetric Total Synthesis of Chimonanthine, Folicanthine, and Calycanthine through Double Michael Reaction of Bisoxindole. Angew. Chem. Int. Ed. 2012, 51, 5217–5221; (d) Xie, W.; Jiang, G.; Liu, H.; Hu, J.; Pan, X.; Zhang, H.; Wan, X.; Lai, Y.; Ma, D. Highly Enantioselective Bromocyclization of Tryptamines and Its Application in the Synthesis of (–)-Chimonanthine. Angew. Chem. Int. Ed. 2013, 52, 12924 –12927; (e) Chen, S.-K.; Ma, W.-Q.; Yan, Z.-B.; Zhang, F.-M.; Wang, S.-H.; Tu, Y.-Q.; Zhang, X.-M.; Tian, J.-M. Organo-Cation Catalyzed Asymmetric Homo/Heterodialkylation of Bisoxindoles: Construction of Vicinal All-Carbon Quaternary Stereocenters and Total Synthesis of (−)-Chimonanthidine. J. Am. Chem. Soc. 2018, 140, 10099−10103; (f) Bai, L.; Ma, Y.; Jiang, X. Total Synthesis of (−)-Calycanthine via Iron-Catalyzed Stereoselective Oxidative Dimerization. J. Am. Chem. Soc. 2021, 143, 20609−20615.
- 4For selected reviews, see: (a) Li, S.; Li, X.; Yao, H.; Tan, M.; Xu, D.; Huang N.; Wang, N. Straight-Chain ω-Amino-α,β-Unsaturated Carbonyl Compounds: Versatile Synthons for the Synthesis of Nitrogen- Containing Heterocycles via Organocatalytic Reactions. Org. Chem. Front. 2024, 11, 236–253; (b) Jin, Z.; Zhang, F.; Xiao, X.; Wang, N.; Lv, X.; Zhou, L. Recent Advances in N-Heterocyclic Carbine (NHC)-Catalyzed Fluorination and Fluoroalkylation. Org. Chem. Front. 2024, 11, 2112–2133. For selected examples, see: (c) Huang, Y.; Tan, M.; Wang, N.; Zhang, Y.; Yao, H.; Xiao, X.; Huang, N.; Zou, K. Highly Regio- and Diastereoselective Phosphine-Catalyzed [2 + 4] Annulation of Benzofuran-Derived Azadienes with Allyl Carbonates: Access to Spiro[benzofuran-cyclohexanes]. J. Org. Chem. 2023, 88, 13030–13041; (d) Chen, Z.; Xiong, D.; Wang, N.; Zhang, Y.; Yao, H.; Zhang, J.; Huang, N.; Zou, K. Concise Synthesis of Pyrrolo[3,4-c]quinolines via a P(NMe2)3- Catalyzed [4 + 2] Annulation followed by a Zn/AcOH-Mediated Reduction–Hydroamination–Isomerization. Org. Chem. Front. 2024, 11, 2762–2767; (e) Li, S.; Xu, D.; Yao, H.; Tan, M.; Li, X.; Liu, M.; Wang, L.; Huang, N.; Wang, N. Facile Synthesis of 2-Vinylindolines via a Phosphine-Mediated α-Umpolung/Wittig Olefination/Cyclization Cascade Process. Chem. Commun. 2024, 60, 6773–6776; (f) Li, B.; Hu, X.; Yao, H.; Li, Y.; Xu, D.; Huang, N.; Wang, N. Pyridine-Catalyzed Chemoselective Four-Component Cascade Reaction of Aromatic Aldehydes, Malononitrile/Cyanoacetates, MBH Carbonates and Alcohols. Org. Lett. 2024, 26, 7576−7583.
- 5(a) Overman, L. E.; Paone, D. V.; Stearns, B. A.; Direct Stereo- and Enantiocontrolled Synthesis of Vicinal Stereogenic Quaternary Carbon Centers. Total Syntheses of meso- and (–)-Chimonanthine and (+)-Calycanthine. J. Am. Chem. Soc. 1999, 121, 7702−7703; (b) Ghosh, S.; Chaudhuri, S.; Bisai, A. Catalytic Enantioselective Decarboxylative Allylations of a Mixture of Allyl Carbonates and Allyl Esters: Total Synthesis of (–)- and (+)-Folicanthine. Chem. - Eur. J. 2015, 21, 17479–17484; (c) Babu, K. N.; Roy, A.; Singh, M.; Bisai, A. Thiourea- Catalyzed Enantioselective Malonate Addition onto 3-Sulfonyl-3'- indolyl-2-oxindoles: Formal Total Syntheses of (−)-Chimonanthine, (−)-Folicanthine, and (+)-Calycanthine. Org. Lett. 2018, 20, 6327–6331; (d) Chan, W.-L.; Tang, X.; Zhang, F.; Quek, G.; Mei, G.-J.; Lu, Y. Phosphine-Catalyzed (3+2) Annulation of Isoindigos with Allenes: Enantioselective Formation of Two Vicinal Quaternary Stereogenic Centers. Angew. Chem. Int. Ed. 2019, 58, 6260–6264.
- 6(a) Li, W.; Zhang, J. Phosphine-Triggered Synthesis of Functionalized Cyclic Compounds. Chem. Soc. Rev. 2016, 45, 1657–1677; (b) Ni, H.; Chan, W.-L.; Lu, Y. Phosphine-Catalyzed Asymmetric Organic Reactions. Chem. Rev. 2018, 118, 9344–9411; (c) Guo, H.; Fan, Y. C.; Sun, Z.; Wu, Y.; Kwon, O. Phosphine Organocatalysis. Chem. Rev. 2018, 118, 10049–10293. And references cited therein.
- 7
Zhang, C.; Lu, X. Umpolung Addition Reaction of Nucleophiles to 2,3-Butadienoates Catalyzed by a Phosphine. Synlett 1995, 1995, 645–646.
10.1055/s-1995-5042 Google Scholar
- 8 Chen, Z.; Zhu, G.; Jiang, Q.; Xiao, D.; Cao, P.; Zhang, X. Asymmetric Formation of Quaternary Carbon Centers Catalyzed by Novel Chiral 2,5-Dialkyl-7-phenyl-7-phosphabicyclo-[2.2.1]heptanes. J. Org. Chem. 1998, 63, 5631–5635.
- 9(a) Feng, J.; Huang, Y. Phosphine-Catalyzed (3+2)/(2+3) Sequential Annulation Involving a Triple Nucleophilic Addition Reaction of γ-Vinyl Allenoates. Chem. Commun. 2019, 55, 14011–14014; (b) Feng, J.; Chen, Y.; Qin, W.; Huang, Y. Phosphine-Catalyzed (3 + 2)/(3 + 2) Sequential Annulation of γ-Vinyl Allenoates: Access to Fused Carbocycles. Org. Lett. 2020, 22, 433−437; (c) Feng, J.; Huang, Y. Phosphine-Catalyzed Remote 1,7-Addition for Synthesis of Diene Carboxylates. ACS Catal. 2020, 10, 3541−3547; (d) Li, X.; Huang, Y. Phosphine-Catalyzed Sequential (2+3)/(2+4) Annulation of γ-Vinyl Allenoates: Access to the Synthesis of Chromeno[4,3-b]pyrroles. Chem. Commun. 2021, 57, 9934–9937; (e) Ma, M.; Feng, J.; Cai, W.; Huang, Y. Phosphine-Catalyzed Domino Annulation of γ-Vinyl Allenoates: Synthesis of Tetrahydrofuro[3,2-c]quinoline Derivatives. Org. Lett. 2024, 26, 4037−4042.
- 10 Chen, J.; Cai, Y.; Zhao, G. Asymmetric Michael Addition of Oxindoles to Allenoate Catalyzed by N-Acyl Aminophosphine: Construction of Functionalized Oxindoles with Quaternary Stereogenic Center. Adv. Synth. Catal. 2014, 356, 359–363.
- 11(a) Wang, T.; Yao, W.; Zhong, F.; Pang, G. H.; Lu, Y. Phosphine-Catalyzed Enantioselective ϒ-Addition of 3-Substituted Oxindoles to 2,3-Butadienoates and 2-Butynoates: Use of Prochiral Nucleophiles. Angew. Chem. Int. Ed. 2014, 53, 2964–2968; (b) Wang, T.; Hoon, D. L.; Lu, Y. Enantioselective synthesis of 3-fluoro-3-allyl-oxindoles via phosphine-catalyzed asymmetric γ-addition of 3-fluoro-oxindoles to 2,3-butadienoates. Chem. Commun. 2015, 51, 10186–10189; (c) Tasdan, Y.; Mei, G.-J.; Lu, Y. Enantioselective Synthesis of Mixed 3,3'-Bisindoles via a Phosphine-Catalyzed Umpolung γ-Addition of 3'-Indolyl-3-oxindoles to Allenoates. Sci. Bull. 2020, 65, 557–563; (d) Li, Y.; Bao, H. Radical Transformations for Allene Synthesis. Chem. Sci. 2022, 13, 8491–8506.
- 12(a) Tang, X.; Tan, C. X. A.; Chan, W.-L.; Zhang, F.; Zheng, W.; Lu, Y. Dielectrophilic Allenic Ketone-Enabled [4 + 2] Annulation with 3,3'-Bisoxindoles: Enantioselective Creation of Two Contiguous Quaternary Stereogenic Centers. ACS Catal. 2021, 11, 1361−1367; (b) Khatua, A.; Shyamal, P.; Pal, S.; Mondal, A.; Bisai, A. Concise Total Syntheses of Bis(cyclotryptamine) Alkaloids via Thio-Urea Catalyzed One-Pot Sequential Michael Addition. Chem. Commun. 2022, 58, 3929–3932; (c) Liu, B.; Duan, X.-Y.; Li, J.; Wu, Y.; Li, Y.; Qi, J. N-Heterocyclic Carbene-Catalyzed [3 + 2] Annulation of 3,3'-Bisoxindoles with α-Bromoenals: Enantioselective Construction of Contiguous Quaternary Stereocenters. Org. Lett. 2022, 24, 5929−5934. Also see refs 3c, 3e.
