Lineatin: Difference between revisions

| verifiedrevid = 376399079

| IUPACName = [(1R)-1,3,3-trimethyl-4,6-dioxatricyclo[3.3.1.0^2,7]nonane

| Section1 = {{Chembox Identifiers

| CASNo = 65035-34-9

| PubChem =

| SMILES =

| Section2 = {{Chembox Properties

| Formula = C₁₀H₁₆O₂

| MolarMass = 168.2 g/mol

| Appearance =

| Density =

| MeltingPtC =

| BoilingPt =

| Solubility =

| Section3 = {{Chembox Hazards

| MainHazards =

| FlashPt =

| Autoignition =

'''Lineatin''' is a [[pheromone]] produced by female striped [[ambrosia beetle]], ''Trypodendron lineatum'' Olivier. These kind of beetles is responsible for extensive damage of coniferous forest infestation in Europe and North America. Since lineatin can act as lures used for mass-trapping of ''T. lineatum'', it is being studied to apply as a pest control reagent.

Lineatin was first isolated in 1977 by MacConnell.<ref> {{cite journal |doi=10.1007/BF00989076 |author=MacConnell, J. G.; Borden, J. H.; Silverstein, R. M.; Stokkink, E. |title=Isolation and tentative identification of lineatin, a pheromone from the frass ofTrypodendron lineatum (Coleoptera: Scolytidae) |journal=J Chem. Ecol. |volume=3 |pages=549–561 |year=1977}} </ref>. The [[absolute configuration]] of the biologically active form was later determined as (+)-(1R,4S,5R,7R)-3,3,7-trimethyl-2,9- dioxatricyclo[3.3.1.0^4,7]nonane, whereas other enatinomers process no biological attraction activity.<ref> {{cite journal |doi= 10.1021/jo01300a005 |author= Slessor, K. N.; Oehlschlager, A. C.; Johnston, B. D.; Pierce, H. D.; Grewel, S. K.; Wickremesinghe, L. K. G. |title= Lineatin: regioselective synthesis and resolution leading to the chiral pheromone of Trypodendron lineatum |journal= J. Org. Chem. |volume=45 |pages=2290 |year=1980}} </ref>.

After the absolute structure was determined, lineatin quickly attracted considerable synthetic interests due to its natural occurrence, biological activity, and unique structural features. A few routes describing the [[total synthesis]] of lineatin was proposed with yields of 0.5%-2%. <ref> {{cite journal |doi=10.1016/0040-4020(80)80112-8 |author=Mori, K.; Sasaki, M. |title=Synthesis of racemic and optically active forms of lineatin, the unique tricyclic pheromone of trypodendron lineatum (olivier) |journal=Tetrahedron. |volume=36 |pages=2197–2208 |year=1980}} </ref> <ref> {{cite journal |doi= 10.1016/S0040-4020(01)88680-4 |author= Mori, K.; Uematsu, T.; Minobe, M.; Yanagi, K. |title= Synthesis and absolute configuration of both the enantiomers of lineatin The pheromone of trypodendron lineatum |journal=Tetrahedron. |volume=39 |pages=1735–1743 |year=1983}} </ref> <ref> {{cite journal |doi=10.1021/jo00350a045 |author=Kandil, A. A.; Slessor, K. N. |title=A chiral synthesis of (+)-lineatin, the aggregation pheromone of Trypodendron lineatum (Olivier), from D-ribonolactone |journal= J. Org. Chem. |volume=50 |pages=5649–5655 |year=1985}} </ref> <ref> {{cite journal |author= Mori, K.; Nagano, E. |journal= Liebigs Ann. Chem. |pages=341–344 |year=1991}} </ref>. Recently, a new total synthesis route that adopted a photochemical [2 + 2] [[cycloaddition]] approach to construct diastereoselective cyclobutene and a regiocontrolled oxymercuration reaction was proposed. This route achieved in synthesizing highly pure (+)-lineatin (> 99.5% ee) through 14 steps and resulted in 14% overall yield from a homochiral 2(5H)-furanone. (Figure 1 showed the basic outline of this approach) <ref> {{cite journal |author= Racamonde, M.; Alibes, R.; Figueredo, M.; Font, J.; de March, P. |journal= J. Org. Chem. |volume=73 |pages=5944–5952 |year=2008 |pmid= 18605755 |title= Photochemical cycloaddition of mono-, 1,1-, and 1,2-disubstituted olefins to a chiral 2(5H)-furanone. Diastereoselective synthesis of (+)-lineatin. |issue= 15 |doi= 10.1021/jo800970u}} </ref>.

[[Image:Lineatin_Total_synthesis.gif|none|300px|frame|Figure 1: Lineatin total synthesis.]]

Lineatin is a monoterprene with unique tricyclic acetal structure. Most of the studies regarding lineatin were focused on the total synthesis; little attentions were put on its [[biosynthesis]]. It is suggested that lineatin is derived through oxidation and cyclization of a monoterponid precursor, but no experimental has been done on proving this route. <ref> {{cite journal |author= Vanderwel, D. |journal= PhD thesis. Simon Fraser University |year=1991}} </ref>. Based on its partial structure similarity to [[iridoid]] class of terprenoids, here, a possible biosynthesis pathway was proposed and outlined in figure 2.

[[Image:lineatin route revised.gif|none|300px|width=250|frame|Figure 2: Proposed lineatin biosynthesis pathway.]]

[[Category:Epoxides]]