Catalyst-Free Hydrogenation of Alkenes and Alkynes with Hydrazine in the Presence of Oxygen

Nurettin Menges; Metin Balci

doi:10.1055/s-0033-1340554

Synlett, Table of Contents

Synlett 2014; 25(5): 671-676
DOI: 10.1055/s-0033-1340554

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Catalyst-Free Hydrogenation of Alkenes and Alkynes with Hydrazine in the Presence of Oxygen

Nurettin Menges

^aDepartment of Chemistry, Middle East Technical University, 06531 Ankara, Turkey, Fax: +90(312)2103200 Email: mbalci@metu.edu.tr

^bFaculty of Pharmacy, Yüzüncüyil University, 65080 Van, Turkey

,

Metin Balci*

^aDepartment of Chemistry, Middle East Technical University, 06531 Ankara, Turkey, Fax: +90(312)2103200 Email: mbalci@metu.edu.tr

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Abstract

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Abstract

A series of alkenes and alkynes was subjected to reduction with hydrazine hydrate in ethanol in the presence of oxygen. An efficient method was developed for the reduction of C–C double bonds and C–C triple bonds with diimide, generated in situ from hydrazine hydrate by oxidation with oxygen. The reduction process proceeded for 24–48 hours with high chemoselectivity and excellent yields. This reduction procedure offers synthetic advantages over metal-catalyzed hydrogenation as well as other systems.

Key words

reduction - oxidation - hydrazine - hydrogenation - diimide

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References

References and Notes
1 Mattson B, Foster W, Greimann J, Hoette T, Le N, Mirich A, Wankum S, Cabri A, Reichenbacher C, Schwanke E. J. Chem. Educ. 2013; 613 ; and references therein
2 Bond G. Metal Catalysed Reactions of Hydrocarbons. Springer; New York: 2005
3 Nishimura S. Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis. John Wiley & Sons; New York: 2001

4a Cui X, Burguess K. Chem. Rev. 2005; 105: 3272
4b Handbook of Homogeneous Hydrogenation . de Vries JG, Elsevier CJ. Wiley-VCH; Weinheim: 2007

5a Kollar L, Keglevich G. Chem. Rev. 2010; 110: 4257
5b Alonso F, Riente P, Yus M. Tetrahedron 2009; 65: 10637

6 Furst A, Berlo RC, Hooton S. Chem. Rev. 1965; 65: 51
7 Zhang Y, Chakraborty M, Cerda-Smith CG, Bratton RN, Maurer NE, Senser EM, Novak M. J. Org. Chem. 2013; 78: 6992
8 Huang L, Luo P, Pei W, Liu X, Wang Y, Wang J, Xing W, Huang J. Adv. Synth. Catal. 2012; 354: 2689
9 Nozaki A, Kamegawa T, Ohmichi T, Yamashita H. ChemPhysChem 2013; 14: 2534
10 Imada Y, Kitagawa T, Ohno T, Iida H, Naota T. Org. Lett. 2010; 12: 32

11a Imada I, Iida H, Kitagawa T, Naota T. Chem. Eur. J. 2011; 17: 5908
11b Lamani M, Guralamata RS, Prabhu KR. Chem. Commun. 2012; 48: 6583

12 Kleinke AS, Jamison TF. Org. Lett. 2013; 15: 710

13a Hünig S, Müller HR, Thier W. Angew. Chem. Int. Ed. 1965; 4: 271
13b Miller EC. J. Chem. Educ. 1965; 42: 254

14 Cusack NJ, Reese CB, Risius AC, Roozpeikar B. Tetrahedron 1976; 32: 2157
15 Haukaas MH, O’Doherty GA. Org. Lett. 2002; 4: 1771
16 Hünig S, Müller HR. Angew. Chem. 1962; 74: 215
17 Van Tamelen EE, Dewey RS, Lease MF, Pirkle WH. J. Am. Chem. Soc. 1961; 83: 4302
18 Sutbeyaz Y, Secen H, Balci M. J. Org. Chem. 1988; 53: 2312

19a Balci M. Chem. Rev. 1981; 81: 91
19b Coughlin DJ, Brown RS, Salomon RG. J. Am. Chem. Soc. 1979; 101: 1533
19c Adam W, Eggelte HJ. J. Org. Chem. 1977; 42: 3987

20 Falciola P, Mannino A. Ann. Chim. Appl. 1914; 2: 351
21 Cross BE. J. Chem. Soc. 1960; 3022
22 Corey EJ, Mock WL, Pasto DJ. Tetrahedron Lett. 1961; 347
23 Chen H, Wang J, Hong X, Zhou H.-B, Dong C. Can. J. Chem. 2012; 90: 758
24 Garbish EW. Jr, Schildtcrout SM, Patterson DP, Sprecher CM. J. Am. Chem. Soc. 1965; 87: 2932
25 Simakova IL, Solkina Y, Deliy I, Warna J, Murzin DY. Appl. Catal., A 2009; 356: 216
26 Mirsadeghi S, Rickborn B. J. Org. Chem. 1985; 50: 4340
27 Wu H, Hintermann L. Synthesis 2013; 45: 888
28 Broggi J, Jurcik V, Songis O, Poater A, Cavallo L, Slawin AM. Z, Cazin CS. J. J. Am. Chem. Soc. 2013; 135: 4588
29 Balci M. Basic ¹H and ¹³C NMR Spectroscopy . Elsevier; Amsterdam: 2005: 330
30 Reynolds WF, Peat IR, Hamer GK. Can. J. Chem. 1974; 52: 3415
31 Procedure for hydrogenation: A round-bottom flask was charged with alkene or alkyne (1 mmol) and EtOH (1 mL) [except for cinchonine (3 mL) because of its lower solubility]. To this mixture was added hydrazine monohydrate (4 mmol), then the reaction was placed under an atmosphere of oxygen (balloon). The resulting mixture was stirred at 35 °C for the appropriate time. After consumption of the starting material, the solvent was removed under vacuum and the residue was extracted with EtOAc. The organic phase was dried over MgSO₄ (for isolated products). Volatile products were not isolated and they were analyzed directly by using GC-MS. 1,2,3,4-Tetrahydro-1,4-epoxynaphthalene (16):26 ¹H NMR (400 MHz, CDCl₃): δ = 7.16–7.13 (m, AA′ of AA′BB′, 2 H), 7.09–7.06 (m, BB′ of AA′BB′, 2 H), 5.32 (dd, J = 3.0, 1.8 Hz, 2 H), 2.01–1.95 (m, AA′ of AA′BB′, 2 H), 1.32–1.27 (m, BB′ of AA′BB′, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 145.6, 126.5, 118.7, 78.9, 26.6. (1E,2E)-1,2-Bis[(1-propyl-1H-Pyrrol-2-yl)methylene]hydrazine (29): Obtained as a pale-orange viscous liquid that was recrystallized from MeOH to give a yellow powder (mp 59–60.5 °C). Isolated yield: 89%. ¹H NMR (400 MHz, CDCl₃): δ = 8.40 (br, 2 H), 6.75 (app. t, J = 2.1 Hz, 2 H), 6.56 (br s, 2 H), 6.11 (dd, J = 3.7, 2.6 Hz, 1 H), 4.24 (t, J = 7.2 Hz, 4 H), 1.75 (hext, J = 7.2 Hz, 4 H), 0.85 (t, J = 7.2 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 150.4, 126.5, 125.9, 116.1, 107.4, 49.2, 23.3, 9.7; IR: 2957, 2921, 2856, 1619, 1522, 1460, 1416, 1402, 1368, 1295, 1213, 1065. HRMS: m/z [M + H]⁺ calcd for C₁₆H₂₃N₄: 271.1923; found: 271.1905. 1-(1-Propyl-1H-pyrrol-2-yl)ethanone (27):32 Isolated yield: 91%; dark-brown viscous liquid. ¹H NMR (400 MHz, CDCl₃): δ = 6.96 (dd, J = 4.0, 1.6 Hz, 1 H), 6.85 (app t, J = 2.5 Hz, 1 H), 6.12 (dd, J = 4.0, 2.5 Hz, 1 H), 4.27 (t, J = 7.2 Hz, 2 H), 2.43 (s, 3 H), 1.75 (hext, J = 7.2 Hz, 2 H), 0.89 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 188.2, 130.2, 130.1, 120.2, 107.8, 51.4, 27.3, 24.6, 11.0.
32 Goldberg Y, Abele E, Shymanskaya M. Synth. Commun. 1991; 21: 557