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Synlett 2020; 31(10): 982-986
DOI: 10.1055/s-0040-1708011
DOI: 10.1055/s-0040-1708011
letter
The Use of α-Diazo-γ-butyrolactams in the Büchner–Curtius–Schlotterbeck Reaction of Cyclic Ketones Opens New Entry to Spirocyclic Pyrrolidones
This research was supported by the Russian Foundation for Basic Research (project grant 19-03-00775).Weitere Informationen
Publikationsverlauf
Received: 15. Februar 2020
Accepted after revision: 08. März 2020
Publikationsdatum:
23. März 2020 (online)
ABSTRACT
The only cyclic α-diazocarbonyl compound employed in the Büchner–Curtius–Schlotterbeck ring expansion of cyclic ketones to date was α-diazo-γ-butyrolactone. Encouraged by the recent success using α-diazo acetamides in related Tiffeneau–Demjanov type ring expansions, we extended this approach to various α-diazo-γ-butyrolactams, which produced, under BF3·OEt2-promoted conditions, spirocyclic seven-membered ketones. These findings substantially enhance the possibilities offered by cyclic α-diazocarbonyl compounds in constructing privileged spirocyclic scaffolds for drug design.
KEYWORDS
α-diazocarbonyl compounds - α-diazo-γ-butyrolactams - Büchner–Curtius–Schlotterbeck reaction - ring expansion - spirocyclic 2-pyrrolidonesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1708011.
- Supporting Information
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References and Notes
- 1 Candeias NR, Paterna R, Gois PM. P. Chem. Rev. 2016; 116: 2937
- 2a Buchner E, Curtius T. Ber. Dtsch. Chem. Ges. 1885; 18: 2371
- 2b Schlotterbeck F. Ber. Dtsch. Chem. Ges. 1907; 40: 1826
- 2c Wang Z. Büchner–Curtius–Schlotterbeck Reaction. In Comprehensive Organic Name Reactions and Reagents. John Wiley & Sons, Inc; Weinheim: 2010
- 3 Kontorowski EJ, Kurth MJ. Tetrahedron 2000; 56: 4317
- 4 Moebius DC, Kingsbury JS. J. Am. Chem. Soc. 2009; 131: 878
- 5 Rosenberger M, Yates P. Tetrahedron Lett. 1964; 33: 2285
- 6 Schmitz A, Kraatz U, Korte F. Chem. Ber. 1975; 108: 1010
- 7 Shershnev I, Dar’in D, Chuprun S, Kantin G, Bakulina O, Krasavin M. Tetrahedron Lett. 2019; 60: 1800
- 8a Hashimoto T, Naganawa Y, Maruoka K. J. Am. Chem. Soc. 2011; 133: 8834
- 8b Li W, Tan F, Hao X, Wang G, Tang Y, Liu X, Lin L, Feng X. Angew. Chem. Int. Ed. 2015; 54: 1608
- 8c Liu Z, Sivaguru P, Zanoni G, Anderson EA, Bi X. Angew. Chem. Int. Ed. 2018; 57: 8927
- 9a Zheng Y, Tice CM, Singh SB. Bioorg. Med. Chem. Lett. 2014; 24: 3673
- 9b Zheng Y.-J, Tice CM. Expert Opin. Drug Discovery 2016; 11: 831
- 9c Muller G, Berkenbosch T, Benningshof JC. J, Stumpfe D, Bajorath J. Chem. Eur. J. 2017; 23: 703
- 9d King TA, Stewart HL, Mortensen KT, North AJ. P, Sore HF, Spring DR. Eur. J. Org. Chem. 2019; 5219
- 9e Stotani S, Lorenz C, Winkler M, Medda F, Picazo E, Ortega Martinez R, Karawajczyk A, Sanchez-Quesada J, Giordanetto F. ACS Comb. Sci. 2016; 18: 330
- 9f Lukin A, Kramer J, Hartmann M, Weizel L, Hernandez-Olmos V, Falahati K, Burghardt I, Kalinchenkova N, Bagnyukova D, Zhurilo N, Rautio J, Forsberg M, Ihalainen J, Auriola S, Leppänen J, Konstantinov I, Pogoryelov D, Proschak E, Dar’in D, Krasavin M. Bioorg. Chem. 2018; 80: 655
- 10 Chupakhin E, Babich O, Prosekov A, Asyakina L, Krasavin M. Molecules 2019; 24: 4165
- 11 Chuprun S, Dar’in D, Kantin G, Zhmurov P, Krasavin M. Synlett 2020; 31: 373
- 12a Zhukovsky D, Dar’in D, Kantin G, Krasavin M. Eur. J. Org. Chem. 2019; 2397
- 12b Zhukovsky D, Dar’in D, Krasavin M. Eur. J. Org. Chem. 2019; 4377
- 12c Barkhatova D, Zhukovski D, Dar’in D, Krasavin M. Eur. J. Org. Chem. 2019; 5798
- 12d Eremeyeva, M.; Zhukovski, D.; Dar’in, D.; Krasavin, M.; Beilstein J. Org. Chem., In press.
- 12e Zhukovski D, Dar’in D, Krasavin M. Eur. J. Org. Chem. 2020; DOI: 10.1002/ejoc.202000067.
- 13 General procedure for the preparation of compounds 2a–o: Diazolactam 1 (0.33 mmol) and the respective cyclic ketone (1 mmol) were dissolved in dichloromethane (5 mL) at –78 °C and boron trifluoride diethyl etherate (0.33 mmol, 42 mg) was added to the mixture. The solution was allowed to slowly warm to room temperature and stirred overnight (18 h). The reaction mixture was concentrated to dryness and the residue was purified by column chromatography using ethyl acetate (for N-unsubstituted lactams) or n-hexane/ethyl acetate 3:1 as eluent.
- 14 Characterization data for representative compounds: Compound 2a: Yield: 59 mg (70%); white amorphous solid. 1H NMR (400 MHz, CDCl3): δ = 7.63–7.58 (m, 2 H), 7.40–7.31 (m, 2 H), 7.18–7.11 (m, 1 H), 3.95 (dt, J = 9.3, 7.7 Hz, 1 H), 3.74 (td, J = 9.0, 3.7 Hz, 1 H), 3.09 (ddd, J = 12.4, 11.2, 2.7 Hz, 1 H), 2.86 (ddd, J = 12.6, 7.9, 3.7 Hz, 1 H), 2.55–2.39 (m, 2 H), 2.06–1.94 (m, 2 H), 1.94–1.78 (m, 3 H), 1.66–1.53 (m, 1 H), 1.52–1.39 (m, 1 H), 1.31–1.16 (m, 1 H). 13C NMR (101 MHz, CDCl3): δ = 210.9, 171.9, 139.2, 128.8, 124.8, 120.1, 63.7, 46.3, 41.7, 34.7, 30.4, 28.8, 26.7, 25.3. HRMS (ESI/Q-TOF): m/z [M + H]+ calcd for C16H19NO2: 258.1489; found: 258.1488. Compound 2e: Yield 52 mg (51%); white semi-solid. 1H NMR (400 MHz, CDCl3): δ = 7.56–7.39 (m, 2 H), 7.02–6.73 (m, 2 H), 3.92 (dt, J = 9.4, 7.8 Hz, 1 H), 3.79 (s, 3 H), 3.70 (td, J = 9.1, 3.1 Hz, 1 H), 3.54 (ddd, J = 11.9, 8.1, 5.4 Hz, 1 H), 3.12–3.00 (m, 1 H), 3.11–2.78 (m, 4 H), 2.79–2.69 (m, 1 H), 2.60–2.48 (m, 1 H), 2.19 (ddd, J = 15.3, 7.0, 2.8 Hz, 1 H), 1.83 (ddd, J = 12.8, 8.9, 7.8 Hz, 1 H). 13C NMR (101 MHz, CDCl3): δ = 207.0, 170.9, 156.9, 132.2, 121.9, 114.1, 63.0, 55.5, 46.6, 43.3, 36.4, 28.2, 27.8, 25.3. HRMS (ESI/Q-TOF): m/z [M + Na]+ calcd for C16H19NO3S: 328.0978; found: 328.0970. Compound 2l: Yield: 33 mg (55%); white solid; mp 110.3–111.5 °C. 1H NMR (400 MHz, CDCl3): δ = 6.79 (s, 1 H), 4.09 (ddd, J = 13.0, 6.3, 2.2 Hz, 1 H), 3.94 (ddd, J = 12.2, 6.0, 4.2 Hz, 1 H), 3.66 (ddd, J = 12.4, 9.2, 3.4 Hz, 1 H), 3.56 (ddd, J = 13.0, 9.4, 1.9 Hz, 1 H), 3.46 (dt, J = 9.6, 7.5 Hz, 1 H), 3.36–3.28 (m, 1 H), 3.24 (ddd, J = 13.3, 9.2, 4.3 Hz, 1 H), 2.75 (ddd, J = 12.9, 7.9, 3.7 Hz, 1 H), 2.69–2.53 (m, 2 H), 1.92–1.76 (m, 2 H). 13C NMR (101 MHz, CDCl3): δ = 208.2, 175.8, 68.2, 66.1, 59.7, 45.7, 39.5, 35.4, 32.0. HRMS (ESI/Q-TOF): m/z [M + H]+ calcd for C9H13NO3: 184.0968; found: 184.0972. Compound 2n: Yield: 49 mg (53%); yellow semi-solid. 1H NMR (400 MHz, CDCl3): δ = 6.65–6.46 (m, 1 H), 3.88–3.61 (m, 2 H), 3.61–3.44 (m, 2 H), 3.40 (dt, J = 9.6, 7.5 Hz, 1 H), 3.30 (tdd, J = 9.6, 3.6, 1.2 Hz, 1 H), 3.18 (s, 1 H), 2.76 (ddd, J = 12.9, 7.7, 3.6 Hz, 1 H), 2.70–2.59 (m, 1 H), 2.48–2.36 (m, 1 H), 1.90–1.72 (m, 2 H), 1.46 (s, 9 H). 13C NMR (101 MHz, CDCl3): δ = 207.5, 176.1, 154.7, 80.2, 60.3, 44.1, 43.1, 42.7, 42.4, 41.7, 39.4, 34.5, 34.2, 31.7, 31.4, 28.4. HRMS (ESI/Q-TOF): m/z [M + H]+ calcd for C14H22N2O4: 283.1652; found: 283.1641.
- 15 CCDC 1981753 contains 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/getstructures.
- 16 Regitz M. Justus Liebigs Ann. Chem. 1964; 676: 101
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