Skip to main content
SpringerLink
Log in

Biogenetic-type Synthesis of Terpenoid Systems

  • Chapter
Fortschritte der Chemie Organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products 29

  • 193 Accesses

Abstract

Efforts directed toward the synthesis of naturally occurring cornpounds have, almost from the inception of this kind of work followed two kinds of pathways. The first and for many years the major road travelled was that of total synthesis. Thus the steady accretion of knowlege concerning the structural and stereochemical course of such reactions as base catalyzed condensation, enolate alkylation, and catalytic hydrogenation resulted in the years following the second world war in a series of elegant syntheses of such complex molecules as strychnine, cortisone, chlorophyl, cevine, longifoline, onocerin, germanicol, etc. The alternative approach less well explored until recent years has been the path of biogenetic-type synthesis.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 129.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 169.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 169.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Aebi, A., D. H. R. Barton and A. S. LiNdsev: Sesquiterpenoids. Part. Iii The Stereochemistry of Caryophyllene. J. Chem. Soc. (London) 1953 3124.

    Google Scholar 

  2. Barton, D. H. R., O. C. Brockman and P. DE Mayo: Sesquiterpenoids. Part Xii. Further investigations on the Chemistry of Pyrethrosin. J. Chem. Soc. (London) 196o, 2263.

    Google Scholar 

  3. Barton, D. H. R. and K. H. Overton: Triterpenoids. Part XX. The Constitution and Stereochemistry of a Novel Tetracyclic Triterpenoid. J. Chem. Soc. (London) 19572639.

    Google Scholar 

  4. Breslow, R., E. Barrett and E. MoHacst: Free Radical Additions to Squalene. Tetrahedron Lett. 1962, 1207.

    Google Scholar 

  5. Breslow, R., J. T. Groves and S. S. Olin: A Novel Terpene Cyclization: Tetrahedron Lett. 1966, 4717.

    Google Scholar 

  6. Breslow, R., S. S. Olin and J. T. Groves: Oxidative Cyclization of Farnesyl Acetate by a Free Radical Path. Tetrahedron Lett. 1968, 1837.

    Google Scholar 

  7. ChavVla, A. and S. Den: A New Class of Triterpenoids from Ailanthus Mala-barica DC. Derivatives of Malabaracane. Tetrahedron Lett. 1967 4837.

    Google Scholar 

  8. S. Clayton, R. B.: Biosynthesis of Sterols, Steroids and Terpenoids. Part I. Biogenesis of Cholesterol and the Fundamental Steps in Terpenoid Biosynthesis. Quart. Rev. (London) 19, 168 (1965).

    Google Scholar 

  9. Corey, E. J., N. N. Girobra and C. T. Mathew: Total Synthesis of dl-Cedrene and di-Cedrol. J. Amer. Chem. Soc. 91, 1557 (1969).

    Google Scholar 

  10. Cornborth, J. W.: Olefin Alkylation in Biosynthesis. Angey’. Chem. Internat. Edit. 7, 903 (1968).

    Google Scholar 

  11. Crandall, T. G. and R. G. Lawton: A Biogenetic-Type Synthesis of Cedrene. J. Amer. Chem. Soc. 91, 2127ss (1969).

    Google Scholar 

  12. Dittman, W. und F. Sturzenhofecker Synthese von racer. (i S: 45: 9 R) (i R 4R:9 S)-cis-Decalindiol-(I.4). Liebigs Ann. Chem. 688, 57 (1965).

    Google Scholar 

  13. Eschenmoser, A., D. Felix, M. Gut, J. Meier and P. Stadler: Some Aspects of Acid Catalyzed Cyclizations of Terpenoid Polyenes. Ciba Foundation Symposium on the Biosynthesis of Terpenes and Sterols, p. 217. G. E. W. Wolstenholme and M. O’Conner, Ed. London: J. and A. Churchill, Ltd. 1959.

    Google Scholar 

  14. Eschenmoser, A., L. Ruzicka, O. Jeder und D. Arigoni: Zur Kenntnis der Terpene. 190. Mitt. Eine stereochemische Interpretation der biogenetischen isoprenregel bei den Triterpcn. Hely. Chim. Acta 38, 1268 (1955).

    Google Scholar 

  15. Fairlie, J. C., G. L. Hodgson and T. Money: Biogenetic-Type Synthesis of Camphor. Chem. Comm. 1969, 1196.

    Google Scholar 

  16. Fazakerley, H., T. G. Halsall and E. R. H. Jones: The Chemistry of Triter-penes and Related Compounds. Part Xxxiv. The Structure of Hydroxyhopanone. J. Chem. Soc. (London) 1959. 1877.

    Google Scholar 

  17. Goldsmith, D. J.: The Cyclization of Epoxyolefins: The Reaction of Geraniolene Monoepoxide with Boron Fluoride Etherate. J. Amer. Chem. Soc. 84, 3913 (1962).

    Google Scholar 

  18. Goldsmith, D. J.: Unpublished observations.

    Google Scholar 

  19. GoLnsaItu, D. J. and B. C. Clark, Jr.: The Cyclization of Epoxyolefins. V. A Model for the Synthesis of the Diterpene Acids. Tetrahedron Lett. 1967, 1215.

    Google Scholar 

  20. Goldsmith, D. J., B. C. Clark, Jr. and R. C. JoInes: The Cyclization of Epoxy-olefins. Iii. The Formation of Bridged Systems: Tetrahedron Lett. 1966, 1149.

    Google Scholar 

  21. Goldsmith, D. J., B. C. Clark, Jr. and R. C. JoIxEs: The Cyclization of Epoxy-olefins. I V. Bicyclic Ethers from a Citronellal Derivative. Tetrahedron Lett. 1967, 1211.

    Google Scholar 

  22. Goldsmith, D. J. and J. E. Evans: Unpublished observations.

    Google Scholar 

  23. Goldsmith, D. J. and C. F. Phillips: The Structural and Stcreochenmieal Course of iu 01110 Epoxy Olefin Cyclization. Diterpenoid Intermediates. J. Amer. Chem. Soc. 91, 5862 (1969).

    Article  CAS  Google Scholar 

  24. Haley, R. C., J. A. Miller and H. C. S. ACoon: Phosphate Esters. Part II. The Formation of 3Ionoterpene Hydrocarbons from Geranyl and Xeryl Biphenyl Phosphates. J. Cheng. Soc. ( London) (C ) 1969, 264.

    Google Scholar 

  25. HoRZ, W., D. Melciiior, R. N. 3Iirrington and P. S. P2Z-V-ELs: Resin Acids. 11. Cationic Cyclization of Isopimaric Acid Derivatives. Partial Synthesis of lsohilcacne. J. Org. Chem. 30, 1873 (1965).

    Article  Google Scholar 

  26. Ho z, WV’., A. K. Finder and R. A. Iiirrington: Rusin Acids. I1. Cationic Cyclization of Pinuaric Acid Derivatives. Partial Synthesis of (—)-Hlbaene. J. Org. Chem. 31, 2257 (1966).

    Article  Google Scholar 

  27. Johnson, W. S.: Monenzymic Iiogenetic-like Olefinic Cyclizations. Accounts Chem. Res. I, I (1968).

    Google Scholar 

  28. Johnson, S. S.: Recent Studies on the Synthesis of Hnmocyclic Systems. Pure and Applied Chem. 7, 317 (1963).

    Google Scholar 

  29. JouNsox, W. S., D. M. 13,vr-EY, R. OA-Y_1NG, R. A. Bell, B. Jaques and J. K. CR Ndall: Cationic C-cIizations Involving Olefinic Bonds. H. Sulvolysis of 5-Hexeny_ l and /cans-5,9-Decadienyl p Nitrobenzcncsulfonates. J. Amer. Chem. Soc. 86, 1959 (19641.

    Google Scholar 

  30. Johnson, W. S., _1. Van Der Gen and J. J. SAyonorA: New Structural and Stercochemical Aspects of the Cyclization of Olefinic 3cetals, J. Amer. cJaan Soc. 89, I7O (1967).

    Google Scholar 

  31. Johnson, A\. S., S. L. Gray, J. R. Crandall and D. _1M. Bailey. Cationic Cyclizations Imegvlpg Olefinic Bonds. Iii. On the Mechanism of Formation of trans-fused Rings. J..Amer. Chem. Soc. 86, 1966 (1964).

    Google Scholar 

  32. S., N. l’. Jensen and J. Hooz: An Efficient Stcrcospccific PoJyolcfinic Cyclization. Total Synthesis of d,1-Fichtelite. J..\.Mer. Chem. Soc. 88, 3859 (1966).

    Google Scholar 

  33. Jonisox, W. S. and R. N. Ninnel: Stcrcospccific. Tricyclization of a yogvogufinic Acctal. J. Amer. Cheng. Soc. 88, 3861 (1966).

    Google Scholar 

  34. Johnson, AV. S., T. 1.1, C. A. Harbert, W. D. Bartlett: ‘6. H. Herrin, B. SrasiciN and D. H. RrcH: Further Developments in the Nonenzymic Bio_enctic-like Steroid Synthesis. J. Amer. Chem. Soc. 92, 4461 (197o).

    Google Scholar 

  35. Al. P. SE1–IM11I,HscI, M. C. S. Sultanbawa and L. A. Dolai’.:.A New Approach to Steroid Total Synthesis. A \onenzymic Biogenetic-Like Olefinic Cyclization Involving-the Stcrcospccific Formation Of Five.,A,ynimetric Centers. J. Amer. Chem. Soc. 90, 2994 (T908).

    Google Scholar 

  36. Jo1Inson, W. S. and T. K. Schaaf: Entry into the l’odocarpene Series through a Biogenetic-like Stercosclective Olefin Cyclization. Chem. Comm. 1969, 611.

    Google Scholar 

  37. 1oHN sox, 1C. S., K. IA IEnnatin, S. P. Brady and G. L. Olson: The Aonuiizviiiiu, Biogenetic-Limc Cyclization of a Tetracnic Acetal. J. Amer. Chem. Soc. 90, 5277 (1968).

    Google Scholar 

  38. Kato, T., S. KANN0 and Y. KIra1LARA: Cyclization of Polrenes. V. Synthesis of t-Chami,grene by the tivclization of cis-and tracas-Mlonocyclofarnesols. Tetrahedron 26, 4z87 (1970).

    Google Scholar 

  39. Nato, T., M. TANEIILR_A, T. Sozr’IÜ and Y. Kitahar.: Biogenetic-type Synthesis of A- and fi-Lcyantenolides. Chem. Comm. 1970, 28.

    Google Scholar 

  40. IyRiiier, ll. 7.., C. A. SalIT, A. V. SEaiEnojsKii, V. S. BogoAnov and \. F. KuCiierov: Cyclization of Isoprenoid Compounds. Communication 20. Cyclization of the Esters of Outarde.Acid under the Influence of Cationic Initiators. Izyestia Akad. Task (Ussr). Sur. Nhim. 1968, 866 (English Translation).

    Google Scholar 

  41. Krimer, M. Z., V. A. Shit, A. V. SemenovsK1I and V. F. Kugheroy: Cyclization of Isoprenoid Compounds. Communication 21. Cyclization of Farnesvlic Esters Under the Action of Cationoid Inutiators.. Izvestia Akad. Nauk (Ussr) Ser. Khim. 1968, 1352 (English translation).

    Google Scholar 

  42. Mccrean1E, T. and K. H. Overton: The Conversion of Labdadienols into Pimara-and Rosadienes. J. Chem. Soc. (C) (London) x971, 312.

    Google Scholar 

  43. Mccreadie, T., K. I-l. Overton and A. J. Allison: A Synthesis of Rosenonolactone and Deoxyrosenonolactone. J. Chem. Soc. ( C) (London ) 1971, 317.

    Google Scholar 

  44. Seneca,:Lan Naeus: Lpistolae 65, 3 (circa 50 AD).

    Google Scholar 

  45. Sharplfss, K. B.: d,1-Malabaricanediol. The First Cyclic Natural Product Derived from Squalene in a \onenzymie Process. J. Amer. Chem. Soc. 92, 6999 (1970).

    Article  Google Scholar 

  46. Shsrpless, K. B.: Synthesis of eryt//ro-IS,19-Dihydroxysqualene-2,3-Oxide and other Internally Oxidized Squalene Derivatives. Chem. Comm. 1970, 1459.

    Google Scholar 

  47. Sharpless, K. B. and E. E. Van Tamelex: Terpenc Terminal Epoxides. Skeletal Rearrangement Accompanying Bicvclization of Squalene 2,3-Oxide. J. Amer. Chem. Soc. 91, 1848 (1969).

    Article  CAS  Google Scholar 

  48. SLlioNsex, J. L. and L. K. Owen: The Terpenes. Vol. I, p. 107 London: Cambridge IEniv. Press. 1947

    Google Scholar 

  49. Smit, V. A., A. V. SEnENovsxII, B. A. Rudenko and V. F. Kl’c]iErov: Cyclization of Isoprenoid Compounds. Communication 8. Mechanism of the Stereo-specific Cyclization of Geranylacetone. Izvestiya Akad. Nauk (Ussr) Ser. lihim. 1963, 1782 (English translation).

    Google Scholar 

  50. Stadler, P. A., A. EscHentilosaR, H. SenIxz and G. SroRK: Entersuchungen fiber den sterischen Verlauf saurekatalysierter Cyclizationen bei terpenoiden Polyenverbindungen. 3. Mitt. Zur Stereochemie der Bicyclofarncsylsäuren. Hely. Chico. Acta 40, 2191 (1957).

    Article  CAS  Google Scholar 

  51. Stork, G. and A. W. Bzrostahler: The Stereochemistry of polvene Cyclization. J. Amer. Chem. Soc. 77, 5086 (19s5).

    Google Scholar 

  52. Stork, G. and J. FieiNi: Intramolecular Cyclization of Unsaturated Diazoketones. J. Anger. Chem. Soc. 83, 4678 (1961).

    Article  CAS  Google Scholar 

  53. Stork, G. and M. Greoson: Aryl Participation in Concerted Cyclization of Cyclopropyl Ketones. J. _Amer. Chem. Soc. 91, 2373 (1969).

    Article  CAS  Google Scholar 

  54. Stork, G., M. Gregson and P. A. Grieco: A Convienient Route to cis and tracas-Trisubstituted Olefins from Geraniol and Nerol. Tetrahedron Lett. 19691391.

    Google Scholar 

  55. Stork, G. and P. A. GirlEco: Olefin Participation in the Acid Catalyzed Opening 02 Acvlcyclopropanes. Tit. Formation of the Bicyclo 2.2.1 heptane System. J. Amer. Chem. Soc. 91, 2407 (1969)

    Article  CAS  Google Scholar 

  56. Stork, G., P. A. Grieco and M. Greoson: Synthesis of Allylic Halides and 1,5-Dienes from Allelic Alcohols. Tetrahedron Lett. 1969, 1393.

    Google Scholar 

  57. Stork, G. and M. Mars: Six-Membered Rings via Olefin Participation in the Opening of Acylcyclopropanones. J. Amer. Chem. Soc. 91, 237 I (1969).

    Google Scholar 

  58. IA:Eaiura, 51., T. Se-zuKI, T. Kato and Y. Kitakara: Synthesis of Levante-policies from Acyclic Progenitor. Tetrahedron Lett. 1970, 1463.

    Google Scholar 

  59. TCnix, T. T. and K. Bloch: On the Mechanism of Cyclization of Squalene. J. Amer. Chem. Soc. 78, 1516 (1956).

    Article  Google Scholar 

  60. Ulery, H. E. and J. H. Richards: The Acid-Catalyzed Cyclization of Acyclic Dienes. J. Amer. Chem. Soc. 86, 3113 (1964).

    Article  CAS  Google Scholar 

  61. Van Tamele:, E. E.: Biogenetic-type Synthesis. Fortschr. Chem. Organ. \aturstoffe 19, 1961.

    Google Scholar 

  62. Van Tamelen, E. E.: Bioorganic Chemistry: Sterols and Acyclic Terpene Terminal Epoxides. Accounts Chem. Res. 1, Iii (1968).

    Article  Google Scholar 

  63. Van Tamelen, E. E. and R. M. Coates: Biogenetic-type Synthesis of (-OEarnesiferol A and (±)-Farnesiferol C. Chem. Comm. 1966, 413.

    Google Scholar 

  64. Van Tamelen, E. E. and T. J. Cdrphey: The Selectiyc in vitro Oxidation of the Terminal Double Bonds in Squalene. Tetrahedron Lett. 1962, 121.

    Google Scholar 

  65. Van Tamelen, E. E. and J. V. McCoRMicrz: Terpene Terminal Epoxides. Mechanistic Aspects of Conversion to the Bicyclic Level. J. Amer. Chem. Soc. 91, 1847 (1969).

    Google Scholar 

  66. Van Tamelen, E. E., G. M. Milne, 31. 1. Suffness, M. C. Rudler, R. J. Anderson and R. S. AcHini: Biogenetic-Type Synthesis of the Isoeuphenol System. J. Amer. Chers. Soc. 92, 7202 (1970).

    Google Scholar 

  67. Van Tamelen, E. E. and J. W. Murphy: Formation of the Lanosterol System through Biogenetic-type Cyclization. J. Amer. Chem. Soc. 92, 7204 (1970).

    Article  Google Scholar 

  68. Van Tamelen, E. E. and R. G. Radeau: Laboratory Cyclization of Geranylgeranyl Acetate Terminal Epoxide. J. Amer. Chem. Soc. 89, 176 (1967).

    Article  Google Scholar 

  69. d’AN Tamelen, E. E., M. A. Schwartz, E. J. Hessler and A Storni: Biogenetic-type Oxidation-Cyclization in the Total Sy nthesis of Triterpenoid Systems. Chem. Comm. 1966, 409.

    Google Scholar 

  70. Van Tamelen, E. E., A. Storni, E. J. Hessler and M. Schwartz: The Blogenetically Patterned in vitro Oxidation-Cyclization of Farnesyl Acetate. J. Amer. Chem. Soc. 85, 3295 (1963).

    Google Scholar 

  71. Van Tamelen, E. E., J. D. Willett, R. B. Clayton and N. E. Lord: Enzymic Conversion of Squalene 2,3-Oxide to Lanosterol and Cholesterol. J. Amer. Chem. Soc. 88, 4752 (1966).

    Article  Google Scholar 

  72. Van Tamelen, E. E., J. Willett, 81. Schwartz and R. Nadeal’: Nollenzymie Laboratory Cyclization of Squalene 2,3-Oxide. J. Amer. Chem. Soc. 88, 5937 (1966).

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Atlanta, Georgia, USA

    D. Goldsmith

Authors
  1. D. Goldsmith
    View author publications

    You can also search for this author in PubMed Google Scholar

Editor information

Editors and Affiliations

  1. Tallahassee, Fla., USA

    W. Herƶ

  2. Freiburg i. Br., Germany

    H. Grisebach

  3. Loughborough, Leics., UK

    G. W. Kirby

Rights and permissions

Reprints and permissions

Copyright information

© 1971 Springer-Verlag Wien

About this chapter

Cite this chapter

Goldsmith, D. (1971). Biogenetic-type Synthesis of Terpenoid Systems. In: Herƶ, W., Grisebach, H., Kirby, G.W. (eds) Fortschritte der Chemie Organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products 29. Fortschritte der Chemie Organischer Naturstoffe / Progress in the Chemistry of Organic Natural Products, vol 29. Springer, Vienna. https://doi.org/10.1007/978-3-7091-3259-3_6

Download citation

  • DOI: https://doi.org/10.1007/978-3-7091-3259-3_6

  • Publisher Name: Springer, Vienna

  • Print ISBN: 978-3-7091-3261-6

  • Online ISBN: 978-3-7091-3259-3

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Search

Navigation