Advertisement

Introduction

  • Lixiong Shao
  • Jianmei Lu
  • Min Shi
Chapter
Part of the SpringerBriefs in Molecular Science book series (BRIEFSMOLECULAR)

Abstract

Vinylidenecyclopropanes (VDCPs) 1, which have strained cyclopropyl group connected with an allene moiety and yet are thermally stable and reactive substances in organic chemistry, are versatile intermediates in organic synthesis. The first synthesis of VDCPs 1 can be traced back to 1959. During the past decades, VDCPs 1 have demonstrated special reactivities, which can be tuned by the electronic or steric effects and nature of the substituents on the skeleton.

Keywords

Organic Synthesis Carbonyl Compound Reactive Substance Steric Effect Special Reactivity 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

References

  1. 1.
    Poutsma ML, Ibarbia PA (1971) Electrophilic additions to 2-methyl-1-(tetramethylcyclopropylidene)propene. Generation of cyclopropylidenecarbinyl cations. J Am Chem Soc 93:440–450CrossRefGoogle Scholar
  2. 2.
    Smadja W (1983) Electrophilic addition to allenic derivatives: chemo-, regio-, and stereochemistry and mechanisms. Chem Rev 83:263–320CrossRefGoogle Scholar
  3. 3.
    Hartzler HD (1959) Carbenes from t-acetylenic chlorides. Synthesis of alkenylidenecyclopropanes. J Am Chem Soc 81:2024–2025CrossRefGoogle Scholar
  4. 4.
    Pasto DJ, Borchardt JK (1976) Carbon-13 nuclear magnetic resonance spectral properties of alkenylidenecyclopropanes. J Org Chem 41:1061–1063CrossRefGoogle Scholar
  5. 5.
    Pasto DJ, Fehlner TP, Schwartz ME, Baney HE (1976) On the orbital interactions of three-membered rings with π systems. Electronic structure of alkenylidenecyclopropanes. J Am Chem Soc 98:530–534CrossRefGoogle Scholar
  6. 6.
    Chapman OL, Gano J, West PR (1981) Acenaphthyne. J Am Chem Soc 103:7033–7036CrossRefGoogle Scholar
  7. 7.
    Zhanpeisov NU, Mizuno K, Anpo M, Leszczynski J (2004) C1–C2 bond cleavage in vinylidenecyclopropanes: theoretical density functional theory study. Int J Quant Chem 96:343–348CrossRefGoogle Scholar
  8. 8.
    Shi M, Shao LX, Lu JM, Wei Y, Mizuno K, Maeda H (2010) Chemistry of vinylidenecyclopropanes. Chem Rev 110:5883–5913CrossRefGoogle Scholar
  9. 9.
    Stang PJ (1978) Unsaturated carbenes. Chem Rev 78:383–405CrossRefGoogle Scholar
  10. 10.
    Stang PJ (1982) Recent developments in unsaturated carbenes and related chemistry. Acc Chem Res 15:348–354CrossRefGoogle Scholar
  11. 11.
    Stang PJ, Ladika M (1981) Extended unsaturated carbenes. Generation, nature, and chemistry of alkatetraenylidenecarbenes, R2C=C=C=C=C=C. J Am Chem Soc 103:6437–6443CrossRefGoogle Scholar
  12. 12.
    Hoffmann RW, Riemann A, Mayer B (1985) Carben-reaktionen, XVIII. Themisches verhalten von 7-alkylidenbicyclo[2.2.1]heptadien-derivaten. Chem Ber 118:2493–2513CrossRefGoogle Scholar
  13. 13.
    Eguchi S, Ikemoto T, Kobayakawa Y, Sasaki T (1985) Mild generation of adamantylidenevinylidene (an alkenylidenecarbene) from 2-bromo-2-(trimethylsilylethynyl)adamantane and (2-bromo-2-trimethylsilylvinylidene)adamantine. J Chem Soc Chem Commun 958–959Google Scholar
  14. 14.
    Sheu JH, Yen CF, Huang CW (1993) The regioselectivity of (dimethylvinylidene)carbene directed by aromatic ring upon the addition into aryl alkenes in the presence of other olefins. J Chin Chem Soc 40:59–65Google Scholar
  15. 15.
    Katsuhira T, Harada T, Oku A (1994) New method for generation of alkenylidenecarbenes from propargylic methanesulfonates and its use in regioselective C–H insertion reactions. J Org Chem 59:4010–4014CrossRefGoogle Scholar
  16. 16.
    Sheu JH, Yen CF, Chan YL, Chung JF (1990) Regioselective cyclopropanation of (dimethylvinylidene)carbene into the α, β-unsaturated double bond of allylic alcohols in the presence of other olefinic groups. J Org Chem 55:5232–5233CrossRefGoogle Scholar
  17. 17.
    Sasaki T, Eguchi S, Ogawa T (1974) Reactions of isoprenoids. XIX. Phase-transfer catalyzed synthesis of dimethylvinylidenecyclopropane derivatives in aqueous medium. J Org Chem 39:1927–1930CrossRefGoogle Scholar
  18. 18.
    Hartzler HD (1964) Vinylidene carbenes by α-elimination from haloallenes. J Org Chem 29:1311–1312CrossRefGoogle Scholar
  19. 19.
    Hennion GF, Motier JF (1969) Substituted acetylenes. LXXXVII. Solvent effects and nucleophile competition in reactions of 3-chloro-3-methyl-1-butyne. J Org Chem 34:1319–1323CrossRefGoogle Scholar
  20. 20.
    Eguchi S, Arasaki M (1988) Synthesis of novel carbo- and heteropolycycles. Part 8. An efficient and convenient synthesis of adamantylidenevinylidenecyclopropane derivatives. J Chem Soc Perkin Trans 1:1047–1050CrossRefGoogle Scholar
  21. 21.
    Sheu JH, Yen CF, Huang CW, Chan YL (1991) Further study on the regioselectivity of (dimethylvinylidene)-carbene uopn the cycloaddition to the α, β-unsaturated double bond of an allylic alcohol and the normal olefinic group. Tetrahedron Lett 32:5547–5550CrossRefGoogle Scholar
  22. 22.
    Sasaki T, Eguchi S, Ohno M, Nakata F (1976) Crown ether catalyzed synthesis of dialkylvinylidenecyclopropane derivatives. J Org Chem 41:2408–2411CrossRefGoogle Scholar
  23. 23.
    Hartzler HD (1961) Carbenes from derivatives of ethynylcarbinols. The synthesis of alkenylidenecyclopropanes. J Am Chem Soc 83:4990–4996CrossRefGoogle Scholar
  24. 24.
    Liese T, de Meijere A (1986) Vielseitige synthese von alkinylcyclopropanen aus olefin-perchlorvinylcarben-addukten. Chem Ber 119:2995–3026CrossRefGoogle Scholar
  25. 25.
    Crombie L, Maddocks PJ, Pattenden G (1978) Monoterpene synthesis via alkenylidenecyclopropanes: acid- and base-catalysed rearrangements. Tetrahedron Lett 19:3479–3482CrossRefGoogle Scholar
  26. 26.
    Maercker A, Wunderlich H, Girreser U (1996) Polylithiumorganic compounds-23. 3,4-Dilithio-1,2-butadienes by addition of lithium metal to 1,4-unsymmetrically substituted butatrienes. Tetrahedron 52:6149–6172CrossRefGoogle Scholar
  27. 27.
    Landor SR, Whiter PF (1965) Allenes. IX. Carbenes from 1-haloallenes. J Chem Soc 5625–5629Google Scholar
  28. 28.
    Patrick TB, Haynie EC, Probst WJ (1972) A comparative study of some reactions of dimethylvinylidene and dimethylmethylidene. J Org Chem 37:1553–1556CrossRefGoogle Scholar
  29. 29.
    Patrick TB, Schmidt DJ (1977) Concerning the nature of dimethylvinylidenecarbene. J Org Chem 42:3354–3356CrossRefGoogle Scholar
  30. 30.
    Landor SR, Patel AN, Whiter PF, Greaves PM (1966) Allenes. XI. The preparation of 3-alkyl- and 3,3-dialkyl-1-bromoallenes. J Chem Soc C 1223–1226Google Scholar
  31. 31.
    Aue DH, Meshishnek MJ (1977) Synthesis and thermal rearrangement of 3-(2′-methyl-prop-1′-enylidene)tricyclo[3.2.1.02,4]oct-6-ene. J Am Chem Soc 99:223–231CrossRefGoogle Scholar
  32. 32.
    Sugita H, Mizuno K, Mori T, Isagawa K, Otsuji Y (1991) Unusual mode of addition of 1,2-alkadienylidene carbenes to 1,3-dienes: 1,4-addition to rigid and flexible 1,3-dienes. Angew Chem Int Ed Engl 30:984–986CrossRefGoogle Scholar
  33. 33.
    Al-Dulayymi J, Baird MS (1988) Highly functionalised carbenes and cyclopropenes from tetrahalocyclopropanes. Tetrahedron Lett 29:6147–6148CrossRefGoogle Scholar
  34. 34.
    Le Perchec P, Conia JM (1970) Etude des rotanes(III) le bicyclopropylidène et sa dimérisation thermique en tétracyclopropylidène. Tetrahedron Lett 11:1587–1588CrossRefGoogle Scholar
  35. 35.
    Denis JM, Le Perchec P, Conia JM (1977) Etude des petits cycles—XXXVII: syntheses et proprietes spectrales du tetracyclopropylidene ([4]rotane) et des composes polycyclopropylspiraniques de la serie. Tetrahedron 33:399–408CrossRefGoogle Scholar
  36. 36.
    Lukin KA, Kozhushkov SI, Andrievsky AA, Ugrak BI, Zefirov NS (1991) Synthesis of branched triangulanes. J Org Chem 56:6176–6179CrossRefGoogle Scholar
  37. 37.
    Isagawa K, Mizuno K, Sugita H, Otsuji Y (1991) J Chem Soc Perkin Trans 1 2283–2285Google Scholar
  38. 38.
    Zöllner S, Buchholz H, Boese R, Gleiter R, de Meijere A (1991) 7,7′-Bi(dispiro[2.0.2.1]heptylidene)—the perspirocyclopropanated bicyclopropylidene. Angew Chem Int Ed Engl 30:1518–1520CrossRefGoogle Scholar
  39. 39.
    Averina EB, Karimov RR, Sedenkova KN, Grishin YK, Kuznetzova TS, Zefirov NS (2006) Carbenoid rearrangement of gem-dihalogenospiropentanes. Tetrahedron 62:8814–8821CrossRefGoogle Scholar
  40. 40.
    Lukin KA, Zefirov NS, Yufit DS, Struchkov YT (1992) Unusual rearrangement of triangulane gem-dibromides in the presence of methyllithium. Tetrahedron 48:9977–9984CrossRefGoogle Scholar
  41. 41.
    Billups WE, Haley MM, Boese R, Bläser D (1994) Synthesis of the bicyclopropenyls. Tetrahedron 50:10693–10700CrossRefGoogle Scholar
  42. 42.
    Keyaniyan S, Gäthling W, de Meijere A (1984) Convenient syntheses of dichloroethenylidenecyclopropanes: precursors to difunctional cyclopropane derivatives. Tetrahedron Lett 25:4105–4108CrossRefGoogle Scholar
  43. 43.
    Northington DJ, Jones WM (1971) Diphenyldiazoallene and diphenylallenyl diazotate. Tetrahedron Lett 12:317–320CrossRefGoogle Scholar
  44. 44.
    Patrick TB (1974) Phase-transfer catalyzed generation of dimethylvinylidene carbene. Tetrahedron Lett 15:1407–1408CrossRefGoogle Scholar
  45. 45.
    Bleiholder F, Shechter H (1964) Substituted dimethylenecyclopropanes. Capture reactions of alkylidene and vinylidene carbenes by allenes. J Am Chem Soc 86:5032–5033CrossRefGoogle Scholar
  46. 46.
    Tsuno T, Sugiyama K (1995) Allenyl(vinyl)methane photochemistry. Photochemistry of 5-[2-(1,2-propadienyl)-substituted alkylidene]-2,2-dimethyl-1,3-dioxane-4,6-diones. Bull Chem Soc Jpn 68:3175–3188CrossRefGoogle Scholar
  47. 47.
    Tsuno T, Sugiyama K (1999) Allenyl(vinyl)methane photochemistry. Photochemistry of methyl 4,4-dimethyl-2,5,6-heptatrienoate derivatives. Bull Chem Soc Jpn 72:519–531CrossRefGoogle Scholar
  48. 48.
    Tsuno T, Sugiyama K (1991) Photochemistry of isopropylidene 3,3,6-trimethyl-1,4,5-heptatriene-1,1-dicarboxylate and its homologues. Chem Lett 20:503–506CrossRefGoogle Scholar
  49. 49.
    Stang PJ, Fisk TE (1979) Extented unsaturated carbenes. Generation and reaction of allenylidene carbenes (R)2C=C=C=C: with olefins. J Am Chem Soc 101:4772–4773CrossRefGoogle Scholar
  50. 50.
    Stang PJ, Fisk TE (1980) Extented unsaturated carbenes. Generation and nature of alkadienylidenecarbenes. J Am Chem Soc 102:6813–6816CrossRefGoogle Scholar
  51. 51.
    de Meijere A, Jaekel F, Simon A, Borrmann H, Köhler J, Johnels D, Scott LT (1991) Regioselective coupling of ethynylcyclopropanes units: hexaspiro[2.0.2.4.2.0.2.4.2.0.2.4]triaconta-7,9,17,19,27,29-hexayne. J Am Chem Soc 113:3935–3941CrossRefGoogle Scholar
  52. 52.
    Manhart S, Schier A, Paul M, Riede J, Schmidbaur H (1995) New organophosphorus ligands: cyclopropanation and other reactions of cumulenes bearing diphenylphosphanyl substituents. Chem Ber 128:365–371CrossRefGoogle Scholar
  53. 53.
    Campbell MJ, Pohlhaus PD, Min G, Ohmatsu K, Johnson JS (2008) An “anti-Baldwin” 3-exo-dig cyclization: preparation of vinylidene cyclopropanes from electron-poor alkenes. J Am Chem Soc 130:9180–9181CrossRefGoogle Scholar
  54. 54.
    Wittig G, Schöllkopf U (1954) Über triphenyl-phosphin-methylene als olefinbildende reagenzien I. Mitteil Chem Ber 97:1318–1330CrossRefGoogle Scholar
  55. 55.
    Edmonds M, Abell A (2004) Modern carbonyl olefination. In: Takeda T (ed) Wiley, Weinheim, pp 1–17Google Scholar
  56. 56.
    Lawrence NJ (1996) Preparation of alkenes. In: Williams JMJ (ed) Oxford University Press, Oxford, pp 19–58Google Scholar
  57. 57.
    Murphy PJ, Brennan J (1988) The Wittig olefination reaction with carbonyl compounds other than aldehydes and ketones. Chem Soc Rev 17:1–30CrossRefGoogle Scholar
  58. 58.
    Maryanoff BE, Reitz AB (1989) The Wittig olefination reaction and modifications involving phosphoryl-stabilized carbanions. Stereochemistry, mechanism, and selected synthetic aspects. Chem Rev 89:863–927CrossRefGoogle Scholar
  59. 59.
    Sandler SR (1977) Chain elongation of alkenes via gem-dihalocyclopropanes: 2-bromo-3, 3-diphenyl-2-propen-1-yl acetate. Org Synth 56:32–35Google Scholar

Copyright information

© The Author(s) 2012

Authors and Affiliations

  1. 1.College of Chemistry and Materials EngineeringWenzhou UniversityWenzhouPeople’s Republic of China
  2. 2.State Key Laboratory of Organometallic ChemistryShanghai Institute of Organic Chemistry, Chinese Academy of SciencesShanghaiPeople’s Republic of China

Personalised recommendations