Concise Report
Design and Application of m-Hydroxybenzyl Alcohols in Regioselective (3 + 3) Cycloadditions of 2-Indolymethanols†
Yi-Cheng Shi,
Xin-Yu Yan,
Ping Wu,
Song Jiang,
Ran Xu,
Wei Tan,
Feng Shi,
Yi-Cheng Shi
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
Search for more papers by this authorXin-Yu Yan
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
Search for more papers by this authorPing Wu
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
Search for more papers by this authorSong Jiang
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
Search for more papers by this authorRan Xu
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
Search for more papers by this authorCorresponding Author
Wei Tan
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorCorresponding Author
Feng Shi
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
School of Petrochemical Engineering, Changzhou University, Changzhou, Jiangsu, 213164 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorYi-Cheng Shi,
Xin-Yu Yan,
Ping Wu,
Song Jiang,
Ran Xu,
Wei Tan,
Feng Shi,
Yi-Cheng Shi
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
Search for more papers by this authorXin-Yu Yan
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
Search for more papers by this authorPing Wu
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
Search for more papers by this authorSong Jiang
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
Search for more papers by this authorRan Xu
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
Search for more papers by this authorCorresponding Author
Wei Tan
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this authorCorresponding Author
Feng Shi
Research Center of Chiral Functional Heterocycles, School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu, 221116 China
School of Petrochemical Engineering, Changzhou University, Changzhou, Jiangsu, 213164 China
E-mail: [email protected]; [email protected]; [email protected]Search for more papers by this author+These authors contributed equally to this work.
† Dedicated to the Special Issue of Emerging Investigators in 2022.
Comprehensive Summary
A new class of m-hydroxybenzyl alcohols has been designed as competent three-carbon building blocks and achieved their application in 2-indolylmethanol-involved regioselective (3 + 3) cycloadditions under the catalysis of Brønsted acids. By this appoach, a series of indole-fused six-membered cycloadducts have been synthesized in overall good yields (up to 98%) with excellent regioselectivity (all >95: 5 rr), thus affording a powerful method for the construction of indole-fused six-membered rings. Moreover, a catalytic asymmetric version of this (3 + 3) cycloaddition has been preliminarily investigated, which revealed the potential of the reaction for constructing chiral indole-fused six-membered rings in an enantioselective manner. This work not only has accomplished the first design of m-hydroxybenzyl alcohols as competent reactants, but also represents the first application of m-hydroxybenzyl alcohols as three-carbon building blocks in cycloadditions. In addition, this work provides a good example for regioselective and C3-nucleophilic (3 + 3) cycloadditions of 2-indolylmethanols, which will substantially enrich the chemistry of 2-indolylmethanols.
Supporting Information
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- 16For recent examples: (a) Li, W.; Xu, X.; Liu, Y.; Gao, H.; Cheng, Y.; Li, P. Enantioselective Organocatalytic 1,6-Addition of Azlactones to para-Quinone Methides: An Access to α,α-Disubstituted and β,β-Diaryl- α-amino Acid Esters. Org. Lett. 2018, 20, 1142–1145; (b) Wang, D.; Song, Z.-F.; Wang, W.-J.; Xu, T. Highly Regio- and Enantioselective Dienylation of p-Quinone Methides Enabled by an Organocatalyzed Isomerization/Addition Cascade of Allenoates. Org. Lett. 2019, 21, 3963–3967; (c) Pan, T.; Shi, P.; Chen, B.; Zhou, D.-G.; Zeng, Y.-L.; Chu, W.-D.; He, L.; Liu, Q.-Z.; Fan, C.-A. CuH-Catalyzed Asymmetric 1,6-Conjugate Reduction of p-Quinone Methides: Enantioselective Synthesis of Triarylmethanes and 1,1,2-Triarylethanes. Org. Lett. 2019, 21, 6397–6402; (d) Li, F.; Chen, X.; Liang, S.; Shi, Z.; Li, P.; Li, W. Organocatalytic Site- and Stereoselective 1,6-Additions of N-Aryl-3- Oxobutanamides to Propargylic aza-p-Quinone Methides. Org. Chem. Front. 2020, 7, 3446–3451; (e) Ali, A.; Jajoria, R.; Harit, H. K.; Singh, R. P. Diastereoselective 1,6-Addition of α-Phosphonyloxy Enolates to para-Quinone Methides. J. Org. Chem. 2022, 87, 5213–5228; (f) Tan, J.-P.; Chen, Y.; Ren, X.; Guo, Y.; Yi, B.; Zhang, H.; Gao, G.; Wang, T. In Situ Phosphonium-Containing Lewis Base-Catalyzed 1,6-Cyanation Reaction: A Facile Way to Obtain α-Diaryl and α-Triaryl Acetonitriles. Org. Chem. Front. 2022, 9, 156–162; (g) Pan, Y.; Ren, W.; Zhang, Z.; Luo, F.; Hou, X.; Li, X.; Yang, Y.-F.; Wang, Y. Tandem 1,6-Addition/Cyclopropanation/Rearrangement Reaction of Vinylogous para-Quinone Methides with 3-Chlorooxindoles: Construction of Vicinal Quaternary Carbon Centers. Org. Chem. Front. 2022, 9, 3697–3708; (h) Yu, K.-Y.; Ge, X.-M.; Fan, Y.-J.; Liu, X.-T.; Yang, X.; Yang, Y.-H.; Zhao, X.-H.; Tao, X.-A.; Fan, C.-A. Iron(III)-Catalyzed Tandem Annulation of Indolyl-Substituted p-Quinone Methides with Ynamides for the Synthesis of Cyclopenta[b]indoles. Chem. Commun. 2022, DOI: https://doi.org/10.1039/D2CC03252J.
- 17For examples of para-alkoxyl- and para-hydroxy benzyl alcohols: (a) Wong, Y. F.; Wang, Z.; Sun, J. Chiral Phosphoric Acid Catalyzed Asymmetric Addition of Naphthols to para-Quinone Methides. Org. Biomol. Chem. 2016, 14, 5751–5754; (b) Yan, J.; Chen, M.; Sung, H. H.-Y.; Williams, I. D.; Sun, J. An Organocatalytic Asymmetric Synthesis of Chiral β,β-Diaryl-α-amino Acids via Addition of Azlactones to In Situ Generated para-Quinone Methides. Chem. Asian J. 2018, 13, 2440–2444; (c) Niu, J.-P.; Nie, J.; Li, S.; Ma, J.-A. Organocatalytic Asymmetric Synthesis of β,β-diaryl Ketones via One-Pot Tandem Dehydration/1,6-Addition/Decarboxylation Transformation of β-keto Acids and 4-Hydroxybenzyl Alcohols. Chem. Commun. 2020, 56, 8687–8690; (d) Li, X.; Duan, M.; Deng, Z.; Shao, Q.; Chen, M.; Zhu, G.; Houk, K. N.; Sun, J. Catalytic Enantioselective Synthesis of Chiral Tetraarylmethanes. Nat. Catal. 2020, 3, 1010–1019; (e) Yan, J.; Zhang, Z.; Chen, M.; Lin, Z.; Sun, J. A Study of the Reactivity of (Aza-)Quinone Methides in Selective C6-Alkylations of Indoles. ChemCatChem 2020, 12, 5053–5057.
- 18(a) Wang, Z.; Zhu, Y.; Pan, X.; Wang, G.; Liu, L. Synthesis of Chiral Triarylmethanes Bearing All-Carbon Quaternary Stereocenters: Catalytic Asymmetric Oxidative Cross-Coupling of 2,2-Diarylacetonitriles and (Hetero)arenes. Angew. Chem. Int. Ed. 2020, 59, 3053–3057; (b) Mao, Y.; Wang, Z.; Wang, G.; Zhao, R.; Kan, L.; Pan, X.; Liu, L. Redox Deracemization of Tertiary Stereocenters Adjacent to An Electron- withdrawing Group. ACS Catal. 2020, 10, 7785–7791; (c) Pan, X.; Wang, Z.; Kan, L.; Mao, Y.; Zhu, Y.; Liu, L. Cross-dehydrogenative Coupling Enables Enantioselective Access to CF3-substituted Allcarbon Quaternary Stereocenters. Chem. Sci. 2020, 11, 2414–2419; (d) Wang, L.; Wang, N.; Qi, Y.; Sun, S.; Liu, X.; Li, W.; Liu, L. Synthesis of Sterically Hindered α-Aminonitriles through 1,6-Azaconjugate Addition of Anilines to δ-Cyano Substituted para-Quinone Methides. Chin. J. Org. Chem. 2020, 40, 3934–3943; (e) Wang, D.; Kan, L.; Ma, Y.; Liu, L. NaOtBu-Catalyzed Hydrophosphonylation of δ-CN-δ-aryldisubstituted para-Quinone Methides with Phosphine Oxides. Chin. J. Org. Chem. 2021, 41, 3192–3203; (f) Liu, X.; Zhao, C.; Zhu, R.; Liu, L. Construction of Vicinal Quaternary Carbon Stereocenters Through Diastereo- and Enantioselective Oxidative 1,6-Conjugate Addition. Angew. Chem. Int. Ed. 2021, 60, 18499–18503.
- 19For examples: (a) Jiang, F.; Yuan, F.-R.; Jin, L.-W.; Mei, G.-J.; Shi, F. Metal-Catalyzed (4+3) Cyclization of Vinyl Aziridines with para-Quinone Methide Derivatives. ACS Catal. 2018, 8, 10234–10240;
(b) Wang, J.-Y.; Zhang, S.; Yu, X.-Y.; Wang, Y.-H.; Wan, H.-L.; Zhang, S.; Tan, W.; Shi, F. Organocatalytic Asymmetric Synthesis of Bioactive Hexahydropyrrolo[2,3-b]indole-Containing Tetrasubstituted Allenes Bearing Multiple Chiral Elements. Tetrahedron Chem 2022, 1, 100007;
10.1016/j.tchem.2022.100007 Google Scholar(c) Wu, P.; Yu, L.; Gao, C.-H.; Cheng, Q.; Deng, S.; Jiao, Y.; Tan, W.; Shi, F. Design and Synthesis of Axially Chiral Aryl-pyrroloindoles via the Strategy of Organocatalytic Asymmetric (2+3) Cyclization. Fund. Res. 2022, DOI: https://doi.org/10.1016/j.fmre.2022.01.002.10.1016/j.fmre.2022.01.002 Google Scholar
- 20For examples: (a) Hang, Q.-Q.; Liu, S.-J.; Yu, L.; Sun, T.-T.; Zhang, Y.-C.; Mei, G.-J.; Shi, F. Design and Application of Indole-Based Allylic Donors for Pd-Catalyzed Decarboxylative Allylation Reactions. Chin. J. Chem. 2020, 38, 1612–1618; (b) Sheng, F.-T.; Li, Z.-M.; Zhang, Y.-Z.; Sun, L.-X.; Zhang, Y.-C.; Tan, W.; Shi, F. Atroposelective Synthesis of 3,3’-Bisindoles Bearing Axial and Central Chirality: Using Isatin-Derived Imines as Electrophiles. Chin. J. Chem. 2020, 38, 583–589; (c) Chen, K.-W.; Chen, Z.-H.; Yang, S.; Wu, S.-F.; Zhang, Y.-C.; Shi, F. Organocatalytic Atroposelective Synthesis of N−N Axially Chiral Indoles and Pyrroles by De Novo Ring Formation. Angew. Chem. Int. Ed. 2022, 61, e202116829; (d) Hang, Q.-Q.; Wu, S.-F.; Yang, S.; Wang, X.; Zhong, Z.; Zhang, Y.-C.; Shi, F. Design and Catalytic Atroposelective Synthesis of Axially Chiral Isochromenone-Indoles, Sci. China Chem. 2022, DOI: 10.1007/s11426-022-1363-y; For a recent review: (e) Zhang, H.-H.; Shi, F. Organocatalytic Atroposelective Synthesis of Indole Derivatives Bearing Axial Chirality: Strategies and Applications, Acc. Chem. Res. 2022, DOI: https://doi.org/10.1021/acs.accounts.2c00465.
- 21 CCDC 2193764 for compound 3aa. See the Supporting Information for details.
- 22For early reviews: (a) Akiyama, T. Stronger Brønsted Acids. Chem. Rev. 2007, 107, 5744–5758; (b) Terada, M. Binaphthol-Derived Phosphoric Acid as A Versatile Catalyst for Enantioselective Carbon–Carbon Bond Forming Reactions. Chem. Commun. 2008, 2008, 4097–4112; (c) Terada, M. Chiral Phosphoric Acids as Versatile Catalysts for Enantioselective Transformations. Chiral Phosphoric Acids as Versatile Catalysts for Enantioselective Transformations. Synthesis 2010, 2010, 1929–1982; For recent reviews: (d) Xia, Z.-L.; Xu-Xu, Q.-F.; Zheng, C.; You, S.-L. Chiral Phosphoric Acid-Catalyzed Asymmetric Dearomatization Reactions. Chem. Soc. Rev. 2020, 49, 286–300; (e) Li, S.; Xiang, S.-H.; Tan, B. Chiral Phosphoric Acid Creates Promising Opportunities for Enantioselective Photoredox Catalysis. Chin. J. Chem. 2020, 38, 213–214; (f) Lin, X.; Wang, L.; Han, Z.; Chen, Z. Chiral Spirocyclic Phosphoric Acids and Their Growing Applications. Chin. J. Chem. 2021, 39, 802–824; (g) Da, B.-C.; Xiang, S.-H.; Li, S.; Tan, B. Chiral Phosphoric Acid Catalyzed Asymmetric Synthesis of Axially Chiral Compounds. Chin. J. Chem. 2021, 39, 1787–1796; For a highlight: (h) Jiang, M.; Zhou, T.; Shi, B. Construction of A New Class of Oxindole-based Axially Chiral Styrenes via Kinetic Resolution. Chin. J. Org. Chem. 2020, 40, 4364–4366.
