Longifolene

Chembox new
Name = (+)-Longifolene
ImageFile = Longifolene.png ImageSize = 100px
ImageName = Longifolene
IUPACName = (1"R",2"S",7"S",9"S")-3,3,7-trimethyl
-8-methylenetricyclo-
[5.4.0.0^2,9] undecane
Section1 = Chembox Identifiers
CASNo = 475-20-7
SMILES = C=C1C3(C)C2CC
C1C2C(C)(C)CCC3
Section2 = Chembox Properties
Formula = C₁₅H₂₄
MolarMass = 204.36 g/mol
Density = 0.928 g/cm³
BoilingPt = 254 °C (706 mm Hg)

Longifolene is the common (or trivial) chemical name of a naturally occurring, oily liquid hydrocarbon found primarily in the high-boiling fraction of certain pine resins. The name is derived from that of a pine species from which the compound was isolated, [Naffa, P.; Ourisson, G. "Bulletin de la Société chimique de France", 1954, 1410.] "Pinus longifolia" (obsolete name for "Pinus roxburghii" Sarg.) [Simonsen, J. L. "J. Chem. Soc." 1920, "117", 570.]

Chemically, longifolene is a tricyclic sesquiterpene. This molecule is chiral, and the enantiomer commonly found in pines and other higher plants exhibits a positive optical rotation of +42.73°. The other enantiomer (optical rotation −42.73°) is found in small amounts in some primitive plants like fungi and liverworts.

Longifolene is used in organic synthesis for the preparation of dilongifolylborane, [Jadhav, P. K.; Brown, H. C. "J. Org. Chem." 1981, "46", 2988.] a chiral hydroborating agent.

Total syntheses

Due to the compact tricyclic structure and lack of functional groups, Longifolene is an attractive target for research groups highlighting new synthetic methodologies. Notable syntheses are by Corey [Corey, E. J. "et al." "J. Am. Chem. Soc." 1961, "83", 1251.] [Corey, E. J. "et al." "J. Am. Chem. Soc." 1964, "86", 478.] , McMurray [McMurray, J. E.; Isser, S. J. "J. Am. Chem. Soc." 1972, "94", 7132.] , Johnson [Volkermann, R. A.; Andrews, G. C.; Johnson, W. S. "J. Am. Chem. Soc." 1975, "97", 4777-4779.] , Oppolzer [Oppolzer, W.; Godel, T. "J. Am. Chem. Soc." 1978, "100", 2584.] , and Schultz [Schultz, A. G. "et al." "J. Org. Chem." 1985, "50", 915.] .

The Johnson biosynthesis has since been validated as feasible using modern quantum mechanical computational methods. The subsequent cationic cascade mechanism has been shown to go through a non-classical cation intermediate. [Ho, Gregory "J. Org. Chem." 2005, "70", 5139 -5143.]

Biosynthesis

The biosynthesis of longifolene begins with farnesyl diphosphate (1) (also called farnesyl pyrophosphate) by means of a cationic polycyclization cascade. Loss of the pyrophosphate group and cyclization by the distal alkene gives intermediate 3, which by means of a 1,3-hydride shift gives intermediate 4. After two additional cyclizations, intermediate 6 produces longifolene by a 1,2-alkyl migration.

References

* Dev, S. "Acc. Chem. Res." 1981, "14", 82-88.