Stereo- and Regioselective [3+2] Cycloaddition of Acetoxy Allenoates with Azides: Metal-Free Synthesis of Multisubstituted Triazoles

Abstract

We have developed a regio- and stereoselective thermal [3+2]-cycloaddition protocol involving acetoxy allenoates as 1,2-dipoles under metal-free conditions for the synthesis of 1,4,5-tri/1,5-disubstituted 1,2,3-triazoles. δ-Acetoxy allenoates act as α- and β-carbon donors and lead to trisubstituted 1,2,3-triazoles with an alkenyl functionality at the 5-position. In sharp contrast to this, β- and γ-carbons participate in the case of β′-acetoxy allenoates to afford 1,5-disubstituted triazole cores. This [3+2] cycloaddition shows a broad substrate scope concerning acetoxy allenoate as well as azide and offers essentially E-stereoisomers in good to high yields. Divergently, the reaction of δ-acetoxy allenoate with trimethylsilyl azide gives an acyclic, nitrogen-inserted product with the cleavage of C–C bonds.

Key words

cycloaddition - regioselectivity - stereoselectivity - acetoxy allenoates - azides

Publication History

Received: 17 July 2021

Accepted after revision: 18 August 2021

Article published online:
12 October 2021

• References

• 1a Zhang C, Lu X. J. Org. Chem. 1995; 60: 2906
• 1b Lu X, Zhang C, Xu Z. Acc. Chem. Res. 2001; 34: 535

Reviews:
• 2a Ye L.-W, Zhou J, Tang Y. Chem. Soc. Rev. 2008; 37: 1140
• 2b Zhao Q.-Y, Lian Z, Wei Y, Shi M. Chem. Commun. 2012; 48: 1724
• 2c Gomez C, Betzer J.-F, Voituriez A, Marinetti A. ChemCatChem 2013; 5: 1055
• 2d Wang Z, Xu X, Kwon O. Chem. Soc. Rev. 2014; 43: 2927
• 2e Kumara Swamy KC, Anitha M, Debnath S, Shankar M. Pure Appl. Chem. 2019; 91: 773
• 2f Li E.-Q, Huang Y. Chem. Commun. 2020; 56: 680
• 3a Xiao H, Chai Z, Zheng C.-W, Yang Y.-Q, Liu W, Zhang J.-K, Zhao G. Angew. Chem. Int. Ed. 2010; 49: 4467
• 3b Sajna KV, Ramesh K, Chakravarty M, Bhuvan Kumar NN, Kumara Swamy KC. J. Org. Chem. 2011; 76: 920
• 3c Zhang Q, Meng L.-G, Zhang J, Wang L. Org. Lett. 2015; 17: 3272
• 3d Li E, Chang M, Liang L, Huang Y. Eur. J. Org. Chem. 2015; 710
• 3e Kumari AL. S, Kumara Swamy KC. J. Org. Chem. 2015; 80: 4084
• 3f Zhou W, Wang H, Tao M, Zhu C.-Z, Lin T.-Y, Zhang J. Chem. Sci. 2017; 8: 4660
• 3g Gan Z, Gong Y, Chu Y, Li E.-Q, Huang Y, Duan Z. Chem. Commun. 2019; 55: 10120
• 3h Shi W, Mao B, Xu J, Wang Q, Wang W, Wu Y, Li X, Guo H. Org. Lett. 2020; 22: 2675
• 3i Liu T, He C, Wang F, Shen X, Li Y, Lang M, Li G, Huang C, Cheng F. Synthesis 2021; 53: 518

See for δ-acetoxy allenoates:
• 4a Zhang Q, Yang L, Tong X. J. Am. Chem. Soc. 2010; 132: 2550
• 4b Hu J, Tian B, Wu X, Tong X. Org. Lett. 2012; 14: 5074
• 4c Zhou W, Ni C, Chen J, Wang D, Tong X. Org. Lett. 2017; 19: 1890
• 4d Xing J.-J, Gao Y.-N, Shi M. Adv. Synth. Catal. 2018; 360: 2552
• 4e Xu T, Wang D, Liu W, Tong X. Org. Lett. 2019; 21: 1944
• 4f Arupula SK, Qureshi AA, Kumara Swamy KC. J. Org. Chem. 2020; 85: 4130
• 4g Zhu Y, Huang Y. Org. Lett. 2020; 22: 6750
• 4h Kumar AS, Chauhan S, Kumara Swamy KC. Org. Lett. 2021; 23: 1123
• 5a Gu Y, Hu P, Ni C, Tong X. J. Am. Chem. Soc. 2015; 137: 6400
• 5b Li F, Chen J, Hou Y, Li Y, Wu X.-Y, Tong X. Org. Lett. 2015; 17: 5376
• 5c Lei Y, Xing J.-J, Xu Q, Shi M. Eur. J. Org. Chem. 2016; 3486
• 5d Dai Z, Zhu J, Wang J, Su W, Yang F, Zhou Q. Adv. Synth. Catal. 2020; 362: 545
• 6a Kallander LS, Lu Q, Chen W, Tomaszek T, Yang G, Tew D, Meek TD, Hofmann GA, Schulz-Pritchard CK, Smith WW, Janson CA, Ryan MD, Zhang G.-F, Johanson KO, Kirkpatrick RB, Ho TF, Fisher PW, Mattern MR, Johnson RK, Hansbury MJ, Winkler JD, Ward KW, Veber DF, Thompson SK. J. Med. Chem. 2005; 48: 5644
• 6b Angell YL, Burgess K. Chem. Soc. Rev. 2007; 36: 1674
• 6c Tam A, Arnold U, Soellner MB, Raines RT. J. Am. Chem. Soc. 2007; 129: 12670
• 6d Ito S, Satoh A, Nagatomi Y, Hirata Y, Suzuki G, Kimura T, Satow A, Maehara S, Hikichi H, Hata M, Kawamoto H, Ohta H. Bioorg. Med. Chem. 2008; 16: 9817
• 6e Tsuritani T, Mizuno H, Nonoyama N, Kii S, Akao A, Sato K, Yasuda N, Mase T. Org. Process Res. Dev. 2009; 13: 1407
• 6f Ito S, Hirata Y, Nagatomi Y, Satoh A, Suzuki G, Kimura T, Satow A, Maehara S, Hikichi H, Hata M. Bioorg. Med. Chem. Lett. 2009; 19: 5310
• 6g Holub JM, Kirshenbaum K. Chem. Soc. Rev. 2010; 39: 1325
• 6h Agalave SG, Maujan SR, Pore VS. Chem. Asian J. 2011; 6: 2696
• 6i Fujinaga M, Yamasaki T, Kawamura K, Kumata K, Hatori A, Yui J, Yanamoto K, Yoshida Y, Ogawa M, Nengaki N, Maeda J, Fukumura T, Zhang M.-R. Bioorg. Med. Chem. 2011; 19: 102
• 6j Valverde IE, Bauman A, Kluba CA, Vomstein S, Walter MA, Mindt TL. Angew. Chem. Int. Ed. 2013; 52: 8957
• 6k Thirumurugan P, Matosiuk D, Jozwiak K. Chem. Rev. 2013; 113: 4905
• 7a Mohammed I, Kummetha IR, Singh G, Sharova N, Lichinchi G, Dang J, Stevenson M, Rana TM. J. Med. Chem. 2016; 59: 7677
• 7b Bonandi E, Christodoulou MS, Fumagalli G, Perdicchia D, Rastelli G, Passarella D. Drug Discovery Today 2017; 22: 1572
• 8a Wang C, Ikhlef D, Kahlal S, Saillard J.-Y, Astruc D. Coord. Chem. Rev. 2016; 316: 1
• 8b Chen Z, Liu Z, Cao G, Li H, Ren H. Adv. Synth. Catal. 2017; 359: 202
• 8c Surendra GR, Anebouselvy K, Ramachary DB. Chem. Asian J. 2020; 15: 2960
• 9a Bleiholder RF, Shechter H. J. Am. Chem. Soc. 1968; 90: 2131
• 9b Wedegaertner DK, Kattak RK, Harrison I, Cristie SK. J. Org. Chem. 1991; 56: 4463
• 9c Ramachary DB, Shashank AB, Karthik S. Angew. Chem. Int. Ed. 2014; 53: 10420
• 9d Sebest F, Casarrubios L, Rzepa HS, White AJ. P, Díez-González S. Green Chem. 2018; 20: 4023
• 9e Giel MC, Smedley CC. J, Mackie ER. R, Guo T, Dong J, Soares da Costa TP, Moses JE. Angew. Chem. Int. Ed. 2020; 59: 1181
• 9f Mali M, Jayaram V, Sharma GV. M, Ghosh S, Berrée F, Dorcet V, Carboni B. J. Org. Chem. 2020; 85: 15104
• 9g Cui X, Zhang X, Wang W, Zhong X, Tan Y, Wang Y, Zhang J, Li Y, Wang X. J. Org. Chem. 2021; 86: 4071
• 9h Majeed K, Wang L, Liu B, Guo Z, Zhou F, Zhang Q. J. Org. Chem. 2021; 86: 207
• 10a Huisgen R. Proc. Chem. Soc., London 1961; 357
• 10b Huisgen R. Angew. Chem. Int. Ed. 1963; 2: 565
• 10c Huisgen R. Angew. Chem. Int. Ed. 1963; 2: 633
• 11a Kolb HC, Finn MG, Sharpless KB. Angew. Chem. Int. Ed. 2001; 40: 2004
• 11b Rostovtsev VV, Green LG, Fokin VV, Sharpless KB. Angew. Chem. Int. Ed. 2002; 41: 2596
• 12 Tornøe CW, Christensen C, Meldal MP. J. Org. Chem. 2002; 67: 3057
• 13a Zhang L, Chen X, Xue P, Sun HH. Y, Williams ID, Sharpless KB, Fokin VV, Jia G. J. Am. Chem. Soc. 2005; 127: 15998
• 13b Boren BC, Narayan S, Rasmussen LK, Zhang L, Zhao H, Lin Z, Jia G, Fokin VV. J. Am. Chem. Soc. 2008; 130: 8923
• 13c Ding S, Jia G, Sun J. Angew. Chem. Int. Ed. 2014; 53: 1877
• 13d Luo Q, Jia G, Sun J, Lin Z. J. Org. Chem. 2014; 79: 11970
• 13e Lal S, Rzepa HS, Díez-González S. ACS Catal. 2014; 4: 2274
• 13f Johansson JR, Beke-Somfai T, Stálsmeden AS, Kann N. Chem. Rev. 2016; 116: 14726
• 13g Liao Y, Lu Q, Chen G, Yu Y, Li C, Huang X. ACS Catal. 2017; 7: 7529
• 13h Song W, Zheng N, Li M, Ullah K, Zheng Y. Adv. Synth. Catal. 2018; 360: 2429
• 13i Song W, Zheng N, Li M, Dong K, Li J, Ullah K, Zheng Y. Org. Lett. 2018; 20: 6705
• 14a Kumaraswamy S, Kommana P, Kumar NS, Kumara Swamy KC. Chem. Commun. 2002; 40
• 14b Chakravarty M, Bhuvan Kumar NN, Sajna KV, Kumara Swamy KC. Eur. J. Org. Chem. 2008; 4500
• 14c Reddy MN, Kumara Swamy KC. Eur. J. Org. Chem. 2012; 2013
• 14d Sajna KV, Kumara Swamy KC. J. Org. Chem. 2012; 77: 8712
• 14e Reddy MN, Kumara Swamy KC. Org. Biomol. Chem. 2013; 11: 7350
• 14f Reddy AS, Reddy MN, Kumara Swamy KC. RSC Adv. 2014; 4: 28359
• 14g Kumari AL. S, Kumara Swamy KC. J. Org. Chem. 2016; 81: 1425
• 15a Pavan MP, Chakravarty M, Kumara Swamy KC. Eur. J. Org. Chem. 2009; 5927
• 15b Gangadhararao G, Tulichala RN. P, Kumara Swamy KC. Chem. Commun. 2015; 51: 7168
• 15c Anitha M, Kumara Swamy KC. Org. Biomol. Chem. 2019; 17: 5736
• 16 CCDC 2097131 (3ff) and 2097132 (7ak) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
• 17 Hurtado-Rodrigo C, Hoehne S, Muňoz MP. Chem. Commun. 2014; 50: 1494
• 18 Selig P, Nghiem T.-L. Synlett 2015; 26: 907