Subscribe to RSS
DOI: 10.1055/s-0030-1259030
Mechanochemical Diels-Alder Cycloaddition Reactions for Straightforward Synthesis of endo-Norbornene Derivatives
Publication History
Publication Date:
10 November 2010 (online)

Abstract
Under mechanochemical milling conditions, Diels-Alder cycloaddition of cyclopentadiene with maleic anhydride and maleimide derivatives proceeded very smoothly, affording endo-norbornenes exclusively in quantitative yield. All the transformations were accomplished at room temperature without using any catalyst or organic solvent, thus the workup and purification procedure is very simple. Control experiments on traditional and other tentative conditions were also investigated.
Key words
norbornenes - mechanochemical milling - solvent-free - cyclopentadiene - Diels-Alder reaction
- Supporting Information for this article is available online:
- Supporting Information (PDF)
- 1
Mamedov EG.Klabunovskii EI. Russ. J. Org. Chem. 2008, 44: 1097 ; and references cited therein - For reviews, see:
- 2a
Novak BM.Risse W.Grubbs RH. Adv. Polym. Sci. 1992, 102: 47Reference Ris Wihthout Link - 2b
Fox MA. Acc. Chem. Res. 1999, 32: 201Reference Ris Wihthout Link - 2c
Buchmeiser MR. Chem. Rev. 2000, 100: 1565Reference Ris Wihthout Link - For some selected examples, see:
- 3a
Fossum RD.Fox MA. J. Am. Chem. Soc. 1997, 119: 1197Reference Ris Wihthout Link - 3b
Maughon BR.Weck M.Mohr B.Grubbs RH. Macromolecules 1997, 30: 257Reference Ris Wihthout Link - 3c
Percec V.Schlueter D. Macromolecules 1997, 30: 5783Reference Ris Wihthout Link - 4
Diels O.Alder K. Justus Liebigs Ann. Chem. 1928, 460: 98Reference Ris Wihthout Link - For reviews, see:
- 5a
Oppolzer W. In Comprehensive Organic Synthesis Vol. 5:Trost BM.Fleming I. Pergamon Press; New York: 1991. p.315Reference Ris Wihthout Link - 5b
Mehta G.Uma R. Acc. Chem. Res. 2000, 33: 278Reference Ris Wihthout Link - 5c
Corey EJ. Angew. Chem. Int. Ed. 2002, 41: 1650Reference Ris Wihthout Link - For selected examples, see:
- 6a
Nakashima D.Yamamoto H. J. Am. Chem. Soc. 2006, 128: 9626Reference Ris Wihthout Link - 6b
Dai M.Sarlah D.Yu M.Danishefsky SJ.Jones GO.Houk KN.
J. Am. Chem. Soc. 2007, 129: 645Reference Ris Wihthout Link - 6c
Hilt G.Danz M. Synthesis 2008, 2257Reference Ris Wihthout Link - Some selected examples for the construction of norbornene moiety via Diels-Alder reaction:
- 7a
Xu X.-P.Ma M.-T.Yao Y.-M.Zhang Y.Shen Q. Eur. J. Inorg. Chem. 2005, 676Reference Ris Wihthout Link - 7b
López I.Silvero G.Arévalo MJ.Babiano R.Palacios JC.Bravo JL. Tetrahedron 2007, 63: 2901Reference Ris Wihthout Link - 7c
Lakner FJ.Negrete GR. Synlett 2002, 643Reference Ris Wihthout Link - For reviews, see:
- 8a
Loupy P. Top. Curr. Chem. 2000, 206: 153Reference Ris Wihthout Link - 8b
Tanaka K.Toda F. Chem. Rev. 2000, 100: 1025Reference Ris Wihthout Link - For some selected examples, see:
- 9a
Hsu C.-C.Lai C.-C.Chiu S.-H. Tetrahedron 2009, 65: 2824Reference Ris Wihthout Link - 9b
Huertas D.Florscher M.Dragojlovic V. Green Chem. 2009, 11: 91Reference Ris Wihthout Link - 9c
Percec V.Schlueter D. Macromolecules 1997, 30: 5783Reference Ris Wihthout Link - 9d
Caputo F.Clerici F.Gelmi ML.Nava D.Pellegrino S. Tetrahedron 2006, 62: 1288Reference Ris Wihthout Link - For reviews, see:
- 10a
Wang G.-W. Fullerene Mechanochemistry, In Encyclopedia of Nanoscience and Nanotechnology Vol. 3:Nalwa HS. American Scientific Publishers; Stevenson Ranch: 2004. p.557Reference Ris Wihthout Link - 10b
Rodríguez B.Bruckmann A.Rantanen T.Bolm C. Adv. Synth. Catal. 2007, 349: 2213Reference Ris Wihthout Link - For some selected examples, see:
- 11a
Balema VP.Wiench JW.Pruski M.Pecharsky VK. J. Am. Chem. Soc. 2002, 124: 6244Reference Ris Wihthout Link - 11b
Rodríguez B.Rantanen T.Bolm C. Angew. Chem. Int. Ed. 2006, 45: 6924Reference Ris Wihthout Link - 11c
Wang G.-W.Wu X.-L. Adv. Synth. Catal. 2007, 349: 1977Reference Ris Wihthout Link - 11d
Gao J.Wang G.-W. J. Org. Chem. 2008, 73: 2955Reference Ris Wihthout Link - 11e
Wang G.-W.Gao J. Org. Lett. 2009, 11: 2385Reference Ris Wihthout Link - 12
Cava MP.Deana AA.Muth K.Mitchell MJ. Org. Synth. Coll., Vol. V Wiley; New York: 1973. p.944 - 14
Canonne P.Bélanger D.Lemay G. J. Org. Chem. 1982, 47: 3953 - 15
Harvey SC. J. Am. Chem. Soc. 1949, 71: 1121 - 16
Kishikawa K.Eida H.Kohmoto S.Yamamoto M.Yamada K. Synthesis 1994, 173 - 17
Morgan MS.Tipson RS.Lowy A.Baldwin WE.
J. Am. Chem. Soc. 1944, 66: 404 - 18
Andrade DE.Nunes RJ.Uieara M. Synth. Commun. 2004, 34: 3073 - 19
Suryanarayana C. Prog. Mater. Sci. 2001, 46: 1
References and Notes
Analytical Data
for Representative Compound
endo
-4-(4-Bromophenyl)-4-aza-tricyclo[5.2.1.0
²,6
]dec-8-ene-3,5-dione
(3e)
Mp 156-157 ˚C. IR (KBr): 2954,
2926, 1711, 1466, 1090, 904, 736, 610 cm-¹. ¹H
NMR (400 MHz, CDCl3): δ = 1.59 (d, J = 8.8 Hz,
1 H), 1.78 (d, J = 8.8
Hz, 1 H), 3.30 (t, J = 8.8 Hz,
2 H), 3.41-3.49 (m, 2 H), 6.24 (s, 2 H), 7.02 (d, J = 8.8 Hz,
2 H), 7.53 (d, J = 8.8
Hz, 2 H). ¹³C NMR (100 MHz, CDCl3): δ = 45.5,
45.8, 52.2, 122.4, 128.1, 130.7, 132.2, 134.6, 176.4. HRMS (FAB+): m/z calcd for C15H12BrNO2 [M+]:
317.0051; found: 317.0049.