Silver-Catalyzed [3+3] Annulation of Glycine Imino Esters with Seyferth–Gilbert Reagent To Access Tetrahydro-1,2,4-triazinecarboxylate Esters

Abstract

A silver-catalyzed protocol for [3+3] annulation of glycine imino esters with Seyferth–Gilbert reagent was developed. A variety of phosphorylated tetrahydro-1,2,4-triazinecarboxylate esters were synthesized in moderate to good yields and with excellent diastereoselectivities. The dehydrogenation of a tetrahydro-1,2,4-triazine product to the corresponding triazine counterpart was also demonstrated.

Key words

[3+3] annulation - glycine imino esters - Seyferth–Gilbert reagent - triazines - phosphorylation

• References and Notes

• 1a Moonen K, Laureyn I, Stevens CV. Chem. Rev. 2004; 104: 6177
• 1b De Clercq E, Holý A. Nat. Rev. Drug Discovery 2005; 4: 928
• 1c Ma J.-A. Chem. Soc. Rev. 2006; 35: 630
• 1d Naydenova ED, Todorov PT, Troev KD. Amino Acids 2010; 38: 23
• 1e Demmer CS, Krogsgaard-Larsen N, Bunch L. Chem. Rev. 2011; 111: 7981
• 1f Elliott TS, Slowey A, Ye Y, Conway SJ. Med. Chem. Commun. 2012; 3: 735
• 1g Romanenko VD, Kukhar VP. Beilstein J. Org. Chem. 2013; 9: 991
• 1h Turcheniuk KV, Kukhar VP, Röschenthaler G.-V, Aceña JL, Soloshonok VA, Sorochinsky AE. RSC Adv. 2013; 3: 6693
• 1i Boissezon R, Muller J, Beaugeard V, Monge S, Robin J.-J. RSC Adv. 2014; 4: 35690
• 2 Pinalli R, Dalcanale E. Acc. Chem. Res. 2013; 46: 399
• 3a Queffélec C, Petit M, Janvier P, Knight DA, Bujoli B. Chem. Rev. 2012; 112: 3777
• 3b Ma Y.-N, Li S.-X, Yang S.-D. Acc. Chem. Res. 2017; 50: 1480

For reviews, see:
• 4a Marinozzi M, Pertusati F, Serpi M. Chem. Rev. 2016; 116: 13991
• 4b Baiju TV, Namboothiri IN. N. Chem. Rec. 2017; 17: 939
• 4c Dhameja M, Pandey J. Asian J. Org. Chem. 2018; 7: 1502
• 5a Ohira S. Synth. Commun. 1989; 19: 561
• 5b Müller S, Liepold B, Roth GJ, Bestmann HJ. Synlett 1996; 521
• 6a Seyferth D, Marmor RS, Hilbert P. J. Org. Chem. 1971; 36: 1379
• 6b Gilbert JC, Giamalva DH. J. Org. Chem. 1992; 57: 4185
• 7a Verma D, Mobin S, Namboothiri IN. N. J. Org. Chem. 2011; 76: 4764
• 7b Marinozzim M, Tondi S, Marcelli G, Giorgi G. Tetrahedron 2014; 70: 9485
• 7c Du T, Du F, Ning Y, Peng Y. Org. Lett. 2015; 17: 1308
• 7d Huang N, Zou L, Peng Y. Org. Lett. 2017; 19: 5806
• 7e Zheng B, Chen H, Zhu L, Hou X, Wang Y, Lan Y, Peng Y. Org. Lett. 2019; 21: 593
• 8a Muruganantham R, Mobin SM, Namboothiri IN. N. Org. Lett. 2007; 9: 1125
• 8b Mohanan K, Martin AR, Toupet L, Smietana M, Vasseur J.-J. Angew. Chem. Int. Ed. 2010; 49: 3196
• 8c Martin AR, Mohanan K, Toupet L, Vasseur J.-J, Smietana M. Eur. J. Org. Chem. 2011; 3184
• 8d Kumar R, Verma D, Mobin SM, Namboothiri IN. N. Org. Lett. 2012; 14: 4070
• 8e Shelke AM, Suryavanshi G. Org. Biomol. Chem. 2015; 13: 8669
• 8f Ahamad S, Gupta AK, Kantc R, Mohanan K. Org. Biomol. Chem. 2015; 13: 1492
• 8g Chaturvedi AK, Kant R, Rastogi N. J. Org. Chem. 2016; 81: 11291
• 8h Gupta AK, Vaishanv NK, Kantc R, Mohanan K. Org. Biomol. Chem. 2017; 15: 6411
• 8i Peng X, Zhang X, Li S, Lu Y, Lan L, Yang C. Org. Chem. Front. 2019; 6: 1775
• 9a Bartnik R, Leśniak S, Wasiak P. Tetrahedron Lett. 2004; 45: 7301
• 9b Ahamad S, Kant R, Mohanan K. Org. Lett. 2016; 18: 280
• 10 Zhai S.-J, Peng X, Zhang F.-G, Ma J.-A. Org. Lett. 2019; 21: 9884

Other phosphorylated-based synthons have also been used for the synthesis of nitrogenous heterocycles; for examples, see:
• 11a Meng J, Wu D, Shi Y, Yu X, Deng W.-P. Tetrahedron 2015; 71: 1074
• 11b Liao L, Zhang H, Zhao X. ACS Catal. 2018; 8: 6745
• 11c Song W, Zheng N, Li M, Ullah K, Zheng Y. Adv. Synth. Catal. 2018; 360: 2429
• 11d Huang N, Tong X, Zhou S, Guo Q, Peng Y. Adv. Synth. Catal. 2019; 361: 4805
• 11e Chalyk BA, Sosedko AS, Volochnyuk DM, Tolmachev AA, Gavrilenko KS, Liashuk OS, Grygorenko OO. Org. Biomol. Chem. 2018; 16: 9152
• 11f Wang L, Ma T, Qiao M, Wu Q, Shi D, Xiao W. Synthesis 2019; 51: 522
• 12a Ma J.-A, Chen Z, Ren N, Zhang F.-G. CN 107935955, 2017
• 12b Ma J.-A, Chen Z, Ren N, Zhang F.-G. CN 107827834, 2017
• 12c Chen Z, Ren N, Ma X, Nie J, Zhang F.-G, Ma J.-A. ACS Catal. 2019; 9: 4600
• 12d Ma J.-A, Tian Y.-C, Zhang F.-G. CN 109956911, 2019
• 13 Zhang L, Chen J.-J, Liu S.-S, Liang Y.-X, Zhao Y.-L. Adv. Synth. Catal. 2018; 360: 2172
• 14a For examples, see: Chen Z, Fan S.-Q, Zheng Y, Ma J.-A. Chem. Commun. 2015; 51: 16545
• 14b Chen Z, Zheng Y, Ma J.-A. Angew. Chem. Int. Ed. 2017; 56: 4569
• 14c Zeng J.-L, Chen Z, Zhang F.-G, Ma J.-A. Org. Lett. 2018; 20: 4562
• 14d Chen Z, Zhang Y, Nie J, Ma J.-A. Org. Lett. 2018; 20: 2120
• 14e Zhang Y, Chen Z, Nie J, Zhang F.-G, Ma J.-A. J. Org. Chem. 2019; 84: 7148
• 14f Peng X, Xiao M.-Y, Zeng J.-L, Zhang F.-G, Ma J.-A. Org. Lett. 2019; 21: 4808
• 14g Zhang Z.-Q, Zheng M.-M, Xue X.-S, Marek I, Zhang F.-G, Ma J.-A. Angew. Chem. Int. Ed. 2019; 58: 18191
• 14h Zhang F.-G, Peng X, Ma J.-A. Youji Huaxue 2019; 39: 109
• 14i Xiao M.-Y, Chen Z, Zhang F.-G, Ma J.-A. Tetrahedron 2020; 76: 131063

Our group has also used diazomethane reagents for other bond-forming reactions, see:
• 15a Qin S, Zheng Y, Zhang F.-G, Ma J.-A. Org. Lett. 2017; 19: 3406
• 15b Zhang F.-G, Lv N, Zheng Y, Ma J.-A. Chin. J. Chem. 2018; 36: 723
• 15c Rong M.-Y, Yang L, Nie J, Zhang F.-G, Ma J.-A. Org. Lett. 2019; 21: 4280
• 15d Guo R, Lv N, Zhang F.-G, Ma J.-A. Org. Lett. 2018; 20: 6994
• 15e Zeng J.-L, Zhang Y, Zheng M.-M, Zhang Z.-Q, Xue X.-S, Zhang F.-G, Ma J.-A. Org. Lett. 2019; 21: 8244
• 16 CCDC 1977600 contains the supplementary crystallographic data for compound 3b. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 17 Methyl 5-(4-Aryl)-6-(diethoxyphosphoryl)-1,4,5,6-tetrahydro-1,2,4-triazine-3-carboxylates 3a–q; General Procedure An oven-dried 10 mL Schlenk tube equipped with a stirring bar and capped with a rubber septum was charged with the appropriate glycine imino ester 1 (1.5 equiv, 0.45 mmol), AgF (0.03 mmol, 10 mol %), and Cs₂CO₃ (1 equiv, 0.30 mmol). The tube was evacuated and backfilled with argon three times. THF (1.5 mL) was transferred into the tube under a positive argon pressure by using a syringe. A solution of Seyferth–Gilbert reagent 2 (1 equiv, 0.3 mmol) in THF (1.5 mL) was then transferred into the mixture by syringe under a positive argon pressure, and the mixture was stirred under argon at rt for 12 h. The mixture was finally concentrated in vacuo in a rotary evaporator and the residue was purified by flash chromatography [silica gel, PE–EtOAc then EtOAc–MeOH (20:1)]. Methyl 5-(4-Chlorophenyl)-6-(diethoxyphosphoryl)-1,4,5,6-tetrahydro-1,2,4-triazine-3-carboxylate (3a) Brown solid; yield: 85.6 mg (73%); mp 120–122 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.34–7.29 (m, 2 H), 7.25–7.21 (m, 2 H), 5.73 (s, 1 H), 5.56 (t, J = 2.2 Hz, 1 H), 4.78–4.83 (m, 1 H), 4.11–3.90 (m, 4 H), 3.86 (s, 3 H), 3.21–3.17 (m, 1 H), 1.24 (t, J = 7.1 Hz, 3 H), 1.12 (t, J = 7.1 Hz, 3 H). ³¹P NMR (162 MHz, CDCl₃): δ = 20.08 (p, J = 8.0 Hz). ¹³C NMR (101 MHz, CDCl₃): δ = 162.1, 138.7 (d, J = 4.5 Hz), 136.2, 134.5, 129.0, 128.8, 63.0 (d, J = 6.7 Hz), 62.7 (d, J = 7.0 Hz), 54.2, 53.1, 52.9 (d, J = 154.1 Hz), 16.5 (d, J = 5.9 Hz), 16.3 (d, J = 6.1 Hz). HRMS (ESI): m/z [M + H]⁺ calcd for C₁₅H₂₂ClN₃O₅P: 390.0980; found: 390.0981.