| 词条 | Longifolene | ||
| 释义 |
| 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- [5.4.0.02,9]undecane |Section1={{Chembox Identifiers | ChEBI_Ref = {{ebicite|changed|EBI}} | ChEBI = 49282 | ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} | ChemSpiderID = 16739255 | SMILES = 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 }} |Section2={{Chembox Properties | Formula = C15H24 | MolarMass = 204.36 g/mol | Density = 0.928 g/cm3 | BoilingPtC = 254 | BoilingPt_notes = (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,[1] Pinus longifolia (obsolete name for Pinus roxburghii Sarg.)[2] 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 certain fungi and liverworts. Longifolene is used in organic synthesis for the preparation of dilongifolylborane,[3] a chiral hydroborating agent. Longifolene is also one of two most abundant aroma constituents of lapsang souchong tea, because the tea is smoked over pine fires.[4] Total synthesesDue 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,[5][6] McMurry,[7] Johnson,[8] Oppolzer,[9] and Schultz.[10] Fallis has published a stereoselective synthesis of (+)-longifolene using an intramolecular Diels-Alder strategy.[11]
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.[12] BiosynthesisThe 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. UseThe borane derivative dilongifolylborane is used in organic synthesis as a chiral hydroborating agent.[13] References1. ^Naffa, P.; Ourisson, G. Bulletin de la Société chimique de France, 1954, 1410. 2. ^Simonsen, J. L. J. Chem. Soc. 1920, 117, 570. 3. ^Jadhav, P. K.; Brown, H. C. J. Org. Chem. 1981, 46, 2988. 4. ^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){{dead link|date=May 2017 |bot=InternetArchiveBot |fix-attempted=yes }} 5. ^{{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}} 6. ^{{cite journal|last1=Corey|first1=E. J.|last2=Ohno|first2=Masaji|last3=Vatakencherry|first3=Paul A.|last4=Mitra|first4=Rajat B.|title=TOTAL SYNTHESIS OF d,l-LONGIFOLENE|journal=Journal of the American Chemical Society|date=March 1961|volume=83|issue=5|pages=1251–1253|doi=10.1021/ja01466a056}} 7. ^{{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}} 8. ^{{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}} 9. ^{{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}} 10. ^{{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}} 11. ^{{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}} 12. ^Ho, Gregory J. Org. Chem. 2005, 70, 5139 -5143. 13. ^{{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}} External links
4 : Alkenes|Sesquiterpenes|Total synthesis|Polycyclic organic compounds |
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