longifolene

{{chembox

| Verifiedfields = changed

| Watchedfields = changed

| verifiedrevid = 438641932

| Name = (+)-Longifolene

| ImageFile = Longifolene plus acsv.svg

| ImageSize = 100px

| ImageName = Longifolene

| IUPACName = (1R,2S,7S,9S)- 3,3,7-trimethyl- 8-methylenetricyclo- [5.4.0.0^2,9]undecane

|Section1={{Chembox Identifiers

| index_label=(+)

| index1_label=(−)

| ChEBI_Ref = {{ebicite|changed|EBI}}

| ChEBI = 49282

| ChEBI1 = 49286

| PubChem = 1796220

| PubChem1 = 1201520

| EC_number = 207-491-2

| UNII = 3YXH7YY8WM

| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}

| ChemSpiderID = 16739255

| ChemSpiderID1 = 1013315

| Beilstein = 5731712 2044263 4663756

| SMILES = C[C@]12CCCC([C@@H]3[C@H]1CC[C@@H]3C2=C)(C)C

| SMILES1 = C[C@@]12CCCC([C@H]3[C@@H]1CC[C@H]3C2=C)(C)C

| StdInChI_Ref = {{stdinchicite|changed|chemspider}}

| StdInChI = 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

| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}

| StdInChIKey = PDSNLYSELAIEBU-GUIRCDHDSA-N

| CASNo_Ref = {{cascite|correct|CAS}}

| CASNo = 475-20-7

| CASNo1 = 16846-09-6

}}

|Section2={{Chembox Properties

| Formula = C₁₅H₂₄

| MolarMass = 204.36 g/mol

| Density = 0.928 g/cm³

| BoilingPtC = 254

| BoilingPt_notes = (706 mm Hg)

}}

|Section7={{Chembox Hazards

| GHSPictograms = {{GHS07}}{{GHS08}}{{GHS09}}

| GHSSignalWord = Danger

| HPhrases = {{H-phrases|304|317|410}}

| PPhrases = {{P-phrases|261|272|273|280|301+310|302+352|321|331|333+313|363|391|405|501}}

}}

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.{{cite book |doi=10.1002/0471238961.2005181602120504.a01.pub2|chapter=Terpenoids |title=Kirk-Othmer Encyclopedia of Chemical Technology |year=2006 |last1=Sell |first1=Charles S. |isbn=0471238961 }} 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.

Occurrence

Terpentine obtained from Pinus longifolia (obsolete name for Pinus roxburghii Sarg.) contains as much as 20% of longifolene.{{Ullmann |doi=10.1002/14356007.a27_267|title=Turpentines |year=2000 |last1=Gscheidmeier |first1=Manfred |last2=Fleig |first2=Helmut |isbn=3527306730 }}

Longifolene is also one of two most abundant aroma constituents of lapsang souchong tea, because the tea is smoked over pinewood fires.[https://web.archive.org/web/20220117091501/https://d.wanfangdata.com.cn/NSTLQK_NSTL_QK10615205.aspx 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)]

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.

Image:Longifolene Biosynthesis Mechanism.png

Synthesis and related chemistry

The laboratory characterization and synthesis of longifolene has long attracted attention.Naffa, P.; Ourisson, G. Bulletin de la Société chimique de France, 1954, 1410.{{cite journal|last1=Corey|first1=E. J.|last2=Ohno|first2=Masaji.|last3=Mitra|first3=Rajat B.|last4=Vatakencherry|first4=Paul A.|title=Total Synthesis of Longifolene|journal=Journal of the American Chemical Society|date=February 1964|volume=86|issue=3|pages=478–485|doi=10.1021/ja01057a039|bibcode=1964JAChS..86..478C }}{{cite journal|last1=McMurry|first1=John E.|last2=Isser|first2=Stephen J.|title=Total synthesis of longifolene|journal=Journal of the American Chemical Society|date=October 1972|volume=94|issue=20|pages=7132–7137|doi=10.1021/ja00775a044|bibcode=1972JAChS..94.7132M }}{{cite journal|last1=Volkmann|first1=Robert A.|last2=Andrews|first2=Glenn C.|last3=Johnson|first3=William S.|title=Novel Synthesis of Longifolene|journal=Journal of the American Chemical Society|date=August 1975|volume=97|issue=16|pages=4777–4779|doi=10.1021/ja00849a062|bibcode=1975JAChS..97.4777V }}{{cite journal|last1=Oppolzer|first1=Wolfgang|last2=Godel|first2=Thierry|title=A New and Efficient Total Synthesis of (.+-.)-longifolene|journal=Journal of the American Chemical Society|date=April 1978|volume=100|issue=8|pages=2583–2584|doi=10.1021/ja00476a071|bibcode=1978JAChS.100.2583O }}{{cite journal|last1=Schultz|first1=Arthur G.|last2=Puig|first2=Salvador|title=The Intramolecular Diene-Carbene Cycloaddition Equivalence and an Enantioselective Birch Reduction-Alkylation by the Chiral Auxiliary Approach. Total Synthesis of (.+-.)- and (−)-Longifolene|journal=The Journal of Organic Chemistry|date=March 1985|volume=50|issue=6|pages=915–916|doi=10.1021/jo00206a049}}{{cite journal|last1=Bo|first1=Lei|last2=Fallis|first2=Alex G.|title=Direct total synthesis of (+)-longifolene via an intramolecular Diels-Alder strategy|journal=Journal of the American Chemical Society|date=May 1990|volume=112|issue=11|pages=4609–4610|doi=10.1021/ja00167a105|bibcode=1990JAChS.112.4609B }}Ho, Gregory J. Org. Chem. 2005, 70, 5139 -5143.

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File:Longifolene total synthesis by Corey.svg

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!Longifolene total synthesis by Corey.svg

It reacts with borane to give the derivative dilongifolylborane, which is a chiral hydroborating agent.{{cite journal | author = Dev, Sukh | title = Aspects of Longifolene chemistry. An example of another Facet of natural products chemistry | journal = Accounts of Chemical Research | year = 1981 | volume = 14 | issue = 3 | pages = 82–88 | doi=10.1021/ar00063a004}}

References

External links

[http://www.synarchive.com/molecule/longifolene Longifolene Total Syntheses @ SynArchive.com]

Category:Polycyclic nonaromatic hydrocarbons

Category:Sesquiterpenes

Category:Total synthesis