Generation of Alkylidene Carbenes through Tetrazole Fragmentation: Recent Advances and Applications in Organic Synthesis

Abstract

Tetrazole fragmentation under mild conditions from 5-hydroxyalkyl-1H-tetrazoles (HATs) or cyanophosphates (CPs) readily generates the corresponding alkylidene carbenes, which undergo [1,2]-rearrangements or [1,5]-C–H insertions to yield one-carbon homologous alkynes or five-membered unsaturated carbocycles, respectively. Furthermore, azido-HATs and 2-cyanoazetidines afford propargylic and homopropargylic amines, respectively, via [1,2]-rearrangement of the corresponding aminoalkyl alkylidene carbenes. These reactions are successfully applied for the synthesis of various biofunctional molecules. This short review summarizes the progress made on this methodology over the last decade.

1 Introduction

2 Early Studies

3 Tetrazole Fragmentation of HATs, Azido-HATs, and 2-Cyanoazetidines

4 HAT Synthetic Methods

5 Tetrazole Fragmentation from CPs

6 Summary and Perspective

Key words

alkylidene carbene - tetrazole - fragmentation - 5-hydroxyalkyl-1H-tetrazole - α-hydroxy-β-azidoalkyl-1H-tetrazoles - 2-cyanoazetidine - cyanophosphate

Publication History

Received: 10 January 2024

Accepted after revision: 02 February 2024

Accepted Manuscript online:
02 February 2024

Article published online:
22 February 2024

• References


For recent reviews on alkylidene carbene chemistry, see:
• 1a Grainger RS, Munro KR. Tetrahedron 2015; 71: 7795
• 1b Kirmse W. Angew. Chem. Int. Ed. 1997; 36: 1164
• 1c Knorr R. Chem. Rev. 2004; 104: 3795
• 2 Jahnke E, Tykwinski RR. Chem. Commun. 2010; 46: 3235
• 3 Habrant D, Rauhala V, Koskinen AM. P. Chem. Soc. Rev. 2010; 39: 2007
• 4a Taber DF. Eur. J. Org. Chem. 2022; e202200032
• 4b Ojeda-Porras AC, Roy V, Agrofoglio LA. Chem. Rec. 2022; 22: e202100307
• 5a Colvin EW, Hamill BJ. J. Chem. Soc., Chem. Commun. 1973; 151
• 5b Colvin EW, Hamill BJ. J. Chem. Soc., Perkin Trans. 1 1977; 869
• 5c Ohira S, Okai K, Moritani T. J. Chem. Soc., Chem. Commun. 1992; 721
• 6a Gilbert JC, Weerasooriya U. J. Org. Chem. 1979; 44: 4997
• 6b Gilbert JC, Giamalva DH, Weerasooriya U. J. Org. Chem. 1983; 48: 5251
• 7a Miwa K, Aoyama T, Shioiri T. Synlett 1994; 107
• 7b Miwa K, Aoyama T, Shioiri T. Synlett 1994; 109
• 7c Miwa K, Aoyama T, Shioiri T. Synlett 1994; 461
• 7d Sakai A, Aoyama T, Shioiri T. Tetrahedron Lett. 2000; 41: 6859
• 7e Yagi T, Aoyama T, Shioiri T. Synlett 1997; 1063
• 8a Ohira S. Synth. Commun. 1989; 19: 561
• 8b Müller S, Liepold B, Roth GJ, Bestmann HJ. Synlett 1996; 521
• 9 Behringer H, Matner M. Tetrahedron Lett. 1966; 7: 1663
• 10 Wardrop DJ, Komenda JP. Org. Lett. 2012; 14: 1548
• 11a Quinodoz P, Lo C, Kletskii M, Burov O, Marrot J, Couty F. Org. Chem. Front. 2015; 2: 492
• 11b Wright K, Quinodoz P, Drouilat B, Couty F. Chem. Commun. 2017; 53: 321
• 11c Tafrioucht A, Rabah J, Baczko K, Fensterbank H, Méallet-Renault R, Clavier G, Couty F, Allard E, Wright K. Dyes Pigm. 2021; 186: 109031
• 12 Quinodoz P, Wright K, Drouilat B, David O, Marrot J, Couty F. Chem. Commun. 2016; 52: 10072
• 13a Yoneyama H, Numata M, Uemura K, Usami Y, Harusawa S. J. Org. Chem. 2017; 82: 5538
• 13b Yoneyama H, Hisaka F, Fujisue D, Usami Y, Zhao Z, Harusawa S. Heterocycles 2018; 96: 106
• 13c Yoneyama H, Uemura K, Usami Y, Harusawa S. Tetrahedron 2017; 73: 6109
• 13d Yoneyama H, Uemura K, Usami Y, Harusawa S. Tetrahedron 2018; 74: 2143
• 13e Yoneyama H, Takatsuji K, Ito A, Usami Y, Harusawa S. Tetrahedron 2021; 82: 131914
• 13f For a review on alkylidene carbene generation from CPs, see: Yoneyama H, Harusawa S. Heterocycles 2018; 96: 2037
• 14a Czernecki S, Valéry J. -M. J. Carbohydr. Chem. 1986; 5: 235
• 14b Pérez-Pérez M.-J, Camarasa MJ. J. Chem. Soc., Chem. Commun. 1992; 1403
• 14c Pérez-Pérez M.-J, Camarasa MJ. Tetrahedron 1994; 50: 7269
• 14d Nguyen Van Nhien A, León R, Postel D, Carmo Carreiras M, Garcia AG. J. Carbohydr. Chem. 2005; 24: 369
• 14e Nguyen Van Nhien A, Cordonnier R, Le Bas M.-D, Delacroix S, Soriano E, Marco-Contelles J, Postel D. Tetrahedron 2009; 65: 9378
• 14f Cordonnier R, Nguyen Van Nhien A, Soriano E, Marco-Contelles J, Postel D. Tetrahedron 2010; 66: 736
• 14g Nguyen Van Nhien A, Soriano E, Marco-Contelles J, Postel D. Carbohydr. Res. 2009; 344: 1605
• 15a Wittenberger SJ, Donner BG. J. Org. Chem. 1993; 58: 4139
• 15b Cantillo D, Gutmann B, Kappe CO. J. Am. Chem. Soc. 2011; 133: 4465
• 16 Quinodoz P, Wright K, Drouillat B, Kletskii ME, Burov ON, Lisovin AV, Couty F. Eur. J. Org. Chem. 2019; 342
• 17a Rostovtsev VV, Green LG, Fokin VV, Sharpless KB. Angew. Chem. Int. Ed. 2002; 41: 2596
• 17b Tornøe CW, Christensen C, Meldal M. J. Org. Chem. 2002; 67: 3057

For recent reviews on tetrazoles, see:
• 18a Bhatt U. Five-Membered Heterocycles with Four Heteroatoms: Tetrazoles . In Modern Heterocyclic Chemistry, Vol. 3. Alvarez-Builla J, Vaquero JJ, Barluenga J. Wiley-VCH; Weinheim: 2011: 1401-1430
• 18b Ostrovski VA, Popova EA, Trifonov RE. Developments in Tetrazole Chemistry (2009–16) . In Advances in Heterocyclic Chemistry, Vol. 123. Scriven E, Ramsden CA. Academic Press; New York: 2017: 1-62
• 19a Satoh Y, Marcopulos N. Tetrahedron Lett. 1995; 36: 1759
• 19b Satoh Y, Moliterni J. Synlett 1998; 528
• 19c Bookser BC. Tetrahedron Lett. 2000; 41: 2805
• 20a Alexakos PD, Wardrop DJ. J. Org. Chem. 2019; 84: 12430
• 20b Dones JM, Abularrage NS, Khanal N, Gold B, Raines RT. J. Am. Chem. Soc. 2021; 143: 9489
• 21 Grammatoglou K, Jirgensons A. J. Org. Chem. 2022; 87: 3810
• 22 Raap R. Can. J. Chem. 1971; 49: 2139
• 23 Wiedemann SH, Bio MM, Brown LM, Hansen KB, Langille NF. Synlett 2012; 23: 2231
• 24 Jones CD, Winter MA, Hirsch KS, Stamm N, Taylor HM, Holden HE, Davenport JD, Krumkalns EV, Suhr RG. J. Med. Chem. 1990; 33: 416
• 25 May BC. H, Abell AD. Tetrahedron Lett. 2001; 42: 5641
• 26a Chandgude AL, Dömling A. Green Chem. 2016; 18: 3718
• 26b Yue T, Wang M.-X, Wang D.-X, Zhu J. Angew. Chem. Int. Ed. 2008; 47: 9454
• 26c Ren Z.-L. Liu J.-C. 2017; 49: 745
• 26d Singh A, Kumar R. Chem. Commun. 2021; 57: 9708
• 27 Fisher BE, Tomson AJ, Horwitz JP. J. Org. Chem. 1959; 24: 1650
• 28a Harusawa S, Yoneda R, Kurihara T, Hamada Y, Shioiri T. Tetrahedron Lett. 1984; 25: 427
• 28b Harusawa S, Yoneda R, Kurihara T, Hamada Y, Shioiri T. Chem. Pharm. Bull. 1983; 31: 2932

For reviews on CPs and DEPC, see:
• 29a Harusawa S, Shioiri T. Tetrahedron 2016; 72: 8125 ; and references cited therein
• 29b Harusawa S. Chem. Pharm. Bull. 2020; 68: 1 ; and references cited therein
• 29c Kurihara T, Harusawa S, Yoneda R. J. Synth. Org. Chem. Jpn. 1988; 46: 1164
• 30a Ohira S, Ida T, Moritani M, Hasegawa T. J. Chem. Soc., Perkin Trans. 1 1998; 293
• 30b Ohira S, Ishii S, Shinohara K, Nozaki H. Tetrahedron Lett. 1990; 31: 1039
• 31a Ghorai S, Lee D. Synthesis 2022; 54: 111
• 31b Lee H.-Y, Kim W.-Y, Lee S. Tetrahedron Lett. 2007; 48: 1407
• 32 Yoneyama H, Oka N, Usami Y, Harusawa S. Tetrahedron Lett. 2020; 61: 151517
• 33a Amagata T, Usami Y, Minoura K, Ito T, Numata A. J. Antibiot. 1997; 51: 33
• 33b Usami Y, Ikura T, Amagata T, Numata A. Tetrahedron: Asymmetry 2000; 11: 3711