Longifolene

Last updated
(+)-Longifolene
Longifolene Longifolene plus acsv.svg
Longifolene
Names
IUPAC name
(1R,2S,7S,9S)- 3,3,7-trimethyl- 8-methylenetricyclo- [5.4.0.02,9]undecane
Identifiers
3D model (JSmol)
5731712 2044263 4663756
ChEBI
ChemSpider
ECHA InfoCard 100.006.812 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • (+):207-491-2
PubChem CID
UNII
  • InChI=1S/C15H24/c1-10-11-6-7-12-13(11)14(2,3)8-5-9-15(10,12)4/h11-13H,1,5-9H2,2-4H3/t11-,12-,13+,15-/m1/s1 X mark.svgN
    Key: PDSNLYSELAIEBU-GUIRCDHDSA-N X mark.svgN
  • (+):C[C@]12CCCC([C@@H]3[C@H]1CC[C@@H]3C2=C)(C)C
  • (−):C[C@@]12CCCC([C@H]3[C@@H]1CC[C@H]3C2=C)(C)C
Properties
C15H24
Molar mass 204.36 g/mol
Density 0.928 g/cm3
Boiling point 254 °C (489 °F; 527 K) (706 mm Hg)
Hazards
GHS labelling:
GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Danger
H304, H317, H410
P261, P272, P273, P280, P301+P310, P302+P352, P321, P331, P333+P313, P363, P391, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Longifolene is a common sesquiterpene. It is an 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. [1] It is a tricyclic chiral molecule. 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 certain fungi and liverworts.

Contents

Occurrence

Terpentine obtained from Pinus longifolia (obsolete name for Pinus roxburghii Sarg.) contains as much as 20% of longifolene. [2]

Longifolene is also one of two most abundant aroma constituents of lapsang souchong tea, because the tea is smoked over pinewood fires. [3]

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.

The biosynthesis of longifolene Longifolene Biosynthesis Mechanism.png
The biosynthesis of longifolene

The laboratory characterization and synthesis of longifolene has long attracted attention. [4] [5] [6] [7] [8] [9] [10] [11]

Longifolene total synthesis by Corey Longifolene total synthesis by Corey.svg
Longifolene total synthesis by Corey
Longifolene total synthesis by Corey

It reacts with borane to give the derivative dilongifolylborane, which is a chiral hydroborating agent. [12]

References

  1. ↑ Sell, Charles S. (2006). "Terpenoids". Kirk-Othmer Encyclopedia of Chemical Technology. doi:10.1002/0471238961.2005181602120504.a01.pub2. ISBN   0471238961.
  2. ↑ Gscheidmeier, Manfred; Fleig, Helmut (2000). "Turpentines". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a27_267. ISBN   3527306730.
  3. ↑ Shan-Shan Yao； Wen-Fei Guo； YI Lu； Yuan-Xun Jiang, "Flavor Characteristics of Lapsang Souchong and Smoked Lapsang Souchong,a Special Chinese Black Tea with Pine Smoking Process", Journal of Agricultural and Food Chemistry, Vol. 53, No.22, (2005)
  4. ↑ Naffa, P.; Ourisson, G. Bulletin de la Société chimique de France, 1954, 1410.
  5. ↑ Corey, E. J.; Ohno, Masaji.; Mitra, Rajat B.; Vatakencherry, Paul A. (February 1964). "Total Synthesis of Longifolene". Journal of the American Chemical Society. 86 (3): 478–485. Bibcode:1964JAChS..86..478C. doi:10.1021/ja01057a039.
  6. ↑ McMurry, John E.; Isser, Stephen J. (October 1972). "Total synthesis of longifolene". Journal of the American Chemical Society. 94 (20): 7132–7137. Bibcode:1972JAChS..94.7132M. doi:10.1021/ja00775a044.
  7. ↑ Volkmann, Robert A.; Andrews, Glenn C.; Johnson, William S. (August 1975). "Novel Synthesis of Longifolene". Journal of the American Chemical Society. 97 (16): 4777–4779. Bibcode:1975JAChS..97.4777V. doi:10.1021/ja00849a062.
  8. ↑ Oppolzer, Wolfgang; Godel, Thierry (April 1978). "A New and Efficient Total Synthesis of (.+-.)-longifolene". Journal of the American Chemical Society. 100 (8): 2583–2584. Bibcode:1978JAChS.100.2583O. doi:10.1021/ja00476a071.
  9. ↑ Schultz, Arthur G.; Puig, Salvador (March 1985). "The Intramolecular Diene-Carbene Cycloaddition Equivalence and an Enantioselective Birch Reduction-Alkylation by the Chiral Auxiliary Approach. Total Synthesis of (.+-.)- and (−)-Longifolene". The Journal of Organic Chemistry. 50 (6): 915–916. doi:10.1021/jo00206a049.
  10. ↑ Bo, Lei; Fallis, Alex G. (May 1990). "Direct total synthesis of (+)-longifolene via an intramolecular Diels-Alder strategy". Journal of the American Chemical Society. 112 (11): 4609–4610. Bibcode:1990JAChS.112.4609B. doi:10.1021/ja00167a105.
  11. ↑ Ho, Gregory J. Org. Chem. 2005, 70, 5139 -5143.
  12. ↑ Dev, Sukh (1981). "Aspects of longifolene chemistry. An example of another Facet of natural products chemistry". Accounts of Chemical Research. 14 (3): 82–88. doi:10.1021/ar00063a004.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.