Longifolene

Last updated
(+)-Longifolene
Longifolene plus acsv.svg
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).
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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.svg Longifolene total synthesis by Corey.svg
Longifolene total synthesis by Corey.svg
Longifolene total synthesis by Corey.svg

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

Related Research Articles

In chemistry, a racemic mixture or racemate is one that has equal amounts of left- and right-handed enantiomers of a chiral molecule or salt. Racemic mixtures are rare in nature, but many compounds are produced industrially as racemates.

<span class="mw-page-title-main">Enantiomer</span> Stereoisomers that are nonsuperposable mirror images of each other

In chemistry, an enantiomer, also known as an optical isomer, antipode, or optical antipode, is one of a pair of molecular entities which are mirror images of each other and non-superposable.

<span class="mw-page-title-main">Lapsang souchong</span> Variety of smoked black tea

Lapsang souchong or Zhengshan xiaozhong is a black tea consisting of Camellia sinensis leaves that is smoke-dried over a pinewood fire. This smoking is accomplished either as a cold smoke of the raw leaves as they are processed or as a hot smoke of previously processed leaves. The intensity of the smoke aroma can be varied by locating the leaves closer or farther from the source of heat and smoke or by adjusting the duration of the process. The flavour and aroma of smoked lapsang souchong is described as containing empyreumatic notes, including wood smoke, pine resin, smoked paprika, and dried longan; it may be mixed with milk but is not bitter and usually not sweetened with sugar. The tea originates from the Wuyi Mountains region of Fujian and is considered a Wuyi tea. It is also produced in Taiwan. It has been labelled as smoked tea, smoky souchong, tarry lapsang souchong and lapsang souchong crocodile. While the tea leaf grading system adopted the term souchong to refer to a particular leaf position, lapsang souchong may be made with any leaf of the Camellia sinensis plant, though it is not unusual for the lower leaves, which are larger and less flavourful, to be used as the smoking compensates for the lower flavour profile and the higher leaves are more valuable for use in unflavoured or unblended teas. In addition to its consumption as a tea, lapsang souchong is also used in stock for soups, stews and sauces or otherwise as a spice or seasoning. Beginning in the early 21st century, an unsmoked variety of lapsang souchong was developed in the village of Tong Mu Guan in the Wuyi mountains. The unsmoked variety has become increasingly popular, particularly in the Chinese domestic market.

<span class="mw-page-title-main">Chirality (chemistry)</span> Geometric property of some molecules and ions

In chemistry, a molecule or ion is called chiral if it cannot be superposed on its mirror image by any combination of rotations, translations, and some conformational changes. This geometric property is called chirality. The terms are derived from Ancient Greek χείρ (cheir) 'hand'; which is the canonical example of an object with this property.

<span class="mw-page-title-main">Enantioselective synthesis</span> Chemical reaction(s) which favor one chiral isomer over another

Enantioselective synthesis, also called asymmetric synthesis, is a form of chemical synthesis. It is defined by IUPAC as "a chemical reaction in which one or more new elements of chirality are formed in a substrate molecule and which produces the stereoisomeric products in unequal amounts."

The Robinson annulation is a chemical reaction used in organic chemistry for ring formation. It was discovered by Robert Robinson in 1935 as a method to create a six membered ring by forming three new carbon–carbon bonds. The method uses a ketone and a methyl vinyl ketone to form an α,β-unsaturated ketone in a cyclohexane ring by a Michael addition followed by an aldol condensation. This procedure is one of the key methods to form fused ring systems.

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<span class="mw-page-title-main">Tröger's base</span> Chemical compound

Tröger's base is a white solid tetracyclic organic compound. Its chemical formula is (CH
3
C
6
H
3
NCH
2
)
2
CH
2
. Tröger's base and its analogs are soluble in various organic solvents and strong acidic aqueous solutions due to their protonation. It is named after Julius Tröger, who first synthesized it in 1887.

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<span class="mw-page-title-main">Geranyl pyrophosphate</span> Chemical compound

Geranyl pyrophosphate (GPP), also known as geranyl diphosphate (GDP), is the pyrophosphate ester of the terpenoid geraniol. Its salts are colorless. It is a precursor to many thousands of natural products.

Farnesyl pyrophosphate (FPP), also known as farnesyl diphosphate (FDP), is the precursor to all sesquiterpenes, which comprises thousand of compounds. These include all sesquiterpenes as well as sterols and carotenoids. It is also used in the synthesis of CoQ, as well as dehydrodolichol diphosphate.

<span class="mw-page-title-main">Galantamine total synthesis</span>

The article concerns the total synthesis of galanthamine, a drug used for the treatment of mild to moderate Alzheimer's disease.

<span class="mw-page-title-main">Sesquiterpene</span> Class of terpenes

Sesquiterpenes are a class of terpenes that consist of three isoprene units and often have the molecular formula C15H24. Like monoterpenes, sesquiterpenes may be cyclic or contain rings, including many combinations. Biochemical modifications such as oxidation or rearrangement produce the related sesquiterpenoids. It is estimated (2006) that 3000 sesquiterpenes have been identified.

<span class="mw-page-title-main">Terpineol</span> Chemical compound

Terpineol is any of four isomeric monoterpenoids. Terpenoids are terpene that are modified by the addition of a functional group, in this case, an alcohol. Terpineols have been isolated from a variety of sources such as cardamom, cajuput oil, pine oil, and petitgrain oil. Four isomers exist: α-terpineol, β-terpineol, γ-terpineol, and terpinen-4-ol. β-Terpineol and γ-terpineol differ only by the location of the double bond. Terpineol is usually a mixture of these isomers with α-terpineol as the major constituent.

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<span class="mw-page-title-main">Bromochlorofluoromethane</span> Chemical compound

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<span class="mw-page-title-main">Ugi's amine</span> Chemical compound

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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) [ permanent dead link ]
  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. 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. 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. 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. 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. 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.