Octenyl

Conjugate addition of vinyllithium or a vinyl Grignard reagent to enones and subsequent oxidation afford the 1.4-diketone 16[25]. 4-Oxopentanals are synthesized from allylic alcohols by [3,3]sigmatropic rearrangement of their vinyl ethers and subsequent oxidation of the terminal double bond. Dihydrojasmone (18) was synthesized from allyl 2-octenyl ether (17) based on Claisen rearrangement and oxidation[25] (page 26). 

Isopinocampheyl(l-isopinocampheyl-2-octenyl)borinic acid (1), available with a diastereomer-ic purity of approximately 80 85% de, reacts smoothly with aldehydes at —15 °C in tetrahy-drofuran to provide a homoallylic alcohol with 79-85% ee after oxidative workup (30% hydrogen peroxide, 40 °C)6. 

The homoaldol products (3S,47T)-(Z)-4-hydroxy-3-methyl-l-octenyl and (35, 4/ )-(Z)-4-hydroxy-3,7-dimethyl-l,6-octadienyl diisopropylcarbamate are easily converted into the naturally occurring y-lactones quercus lactone A1073 and ( + )-eldanolide120, respectively. 

R1 = CHjOTBDMS R2 = CH = CHCHOTBDMS(CHj),CH3 (2S. 3R, 4R )-4- ten-butyldimethylsilyl-oxy)-2-[(fR/lS)-(7)-4-(ten-butyIdimethylsilyloxy)-l-hydroxy-2-octenyl]-3- (E)-7-(tert-butyldimethyl-silyloxy)-3-[(/RlSS)-phenylsul/tnyl -2-heptenyl cyclopentanone yield 70 %... 

The diastereoselective addition of [(S)-3-alkoxy-l-octenyl]lithium to an enantiomerically pure cyclic y-(rer/-butyldimethylsilyloxy)-o(,/S-unsaturated sulfone was employed in the synthesis of ( )-prostaglandin E219, with addition occurring exclusively anti to the sterically demand-... 

The present preparation illustrates a general and convenient method for the fnms-iodopropenylation of an alkyl halide.4 The iodopropenyl-ated material is not usually stable but is a useful synthetic intermediate. For example, it forms a stable crystalline triphenylphosphonium salt for use in the Wittig reaction, and under Kornblum reaction conditions (DMS0-NaHC03, 130°, 3 minutes) it gives an (E)-a,/9-unsaturated aldehyde.4 In addition to the phosphonium salt described in Note 15, the following have been prepared (4-p-methoxyphenyl-2-butenyl)-triphenylphosphonium iodide [Phosphonium, [4-(4-methoxyphenyl)-2-butenyl]triphenyl-, iodide], m.p. 123-127° (2-octenyl)triphenyl-phosphonium iodide [Phosphonium, 2-octenyltriphenyl-, iodide], m.p. 98° and (2-octadecenyl)triphenylphosphonium iodide [Phosphonium, 2-octadecenyltriphenyl-, iodide], m.p. 50°. 

Another stereoselective /1-alkylation was found by Posner and coworkers in the treatment of (S)-( +)-( )- 1-octenyl sulfoxide 190 and (S)-(+)-( )- 1-propenyl sulfoxide... 

Lithium dibutylcuprate reacted with ( )-l, 3-butadienyl p-tosyl sulfone affording (Z)-2-octenyl p-tosyl sulfone. In the reaction of allyl ( )- and (Z)-l, 3-dibutadienyl sulfones with lithium dibutylcuprate or lithium (Z)-di(l-butenyl) cuprate, the major compound obtained was of (Z)-geometry around the 2,3-double bond, indicating that (Z)-selectivity is not so high in this reaction (56-79%)408-... 

C30H34O5 39865-76-4) see Unoprostone isopropyl [3ait-[3aa,4a( ),5p,6aa]]-[l,l -biphenyl]-4-carboxylic acid hexahydro-2-oxo-4-(3-oxo-l-octenyl)-2i/-cyclopen-ta[A]furan-5-yl ester... 

Fig. 10.13. MM2 models of exo and endo cyclization transition structures for 5-hexenyl, 6-heptenyl, and 7-octenyl radicals. Reproduced from Tetrahedron, 41, 3925 (1985), by permission of Elsevier.

Experimentally, this reaction sequence was observed with hydrogen 70) or a substituted octenyl group721 in position 7 of the norbomadiene. In the calculations a methyl group was used as marker, to show the course of the rearrangement. 

CONJUGATE ADDITION OF A VINYLZIRCONIUM REAGENT 3-(1-OCTEN-1-YL)CYCLOPENTANONE (Cyclopentanone, 3-(l-octenyl)-, (E)-)... 

The addition of a large excess of bis(cj-alkenyl)zinc compounds to the TiC -catalyzed polymerization of propene resulted in an increased polymer yield, but a reduction in the molecular weights of the polymers.64 This suggests that the diorganozinc compounds are both co-catalysts and chain-transfer agents in this polymerization. The catalyst activity decreased in the order bis(3-butenyl)zinc < bis(7-octenyl)zinc < chlorodiethylaluminum. Bis(7-octenyl)zinc was co-polymerized with propene to afford hexylzinc side chains, whose zinc-carbon moieties were converted to vinyl groups by the addition of allyl bromide. 

E 1103 Invertase E 1105 Lysozyme E 1200 Polydextrose E 1201 Polyvinylpyrrolidone E 1202 Polyvinylpolypyrrolidone E 1404 Oxidised starch E 1410 Monostarch phosphate E 1412 Distarch phosphate E 1413 Phosphated distarch phosphate E 1414 Acetylated distarch phosphate E 1420 Acetylated starch E 1422 Acetylated distarch adipate E 1440 Hydroxy propyl starch E 1442 Hydroxy propyl distarch phosphate E 1450 Starch sodium octenyl succinate E 1451 Acetylated oxidised starch E 1505 Triethyl citrate E 1518 Glyceryl triacetate (triacetin)... 

R3 = vinyl, (Z)-1 -propenyl, 2-methylpropenyl, ( )-1-octenyl, allenyl, allyl... 

However, in the seed bug family the lygaeid Geocorispunctipes is a predatory species. Females of this species release ( )-2-octenyl acetate, which, while not attractive per se, increases activity levels and stimulates searching behavior of males, with stimulated males dashing towards and investigating small moving objects [35]. 

Females of several species use (R)-5-[(lZ)-l-octenyl]oxacyclopentan-2-one, buibuilactone 69 [ 140-144]. The first y-lactone identified from a scarab beetle was (R)-5-[(Z)-l-decenyl]oxacyclopentan-2-one, japonilure 70, the female produced sex pheromone of the Japanese beetle Popillia japonica [145]. Both 69 and 70 are components of specific blends of several species [140-143]. The Japanese beetle is extremely sensitive to the non-natural enantiomer of his pheromone as little as 1% of the (S)-enantiomer inhibits the attractiveness of the pheromone [ 145]. With respect to species discrimination, this is particularly... 

Hill, C.A.S. and Mallon, S. (1998). The chemical modification of Scots pine with succinic anhydride or octenyl succinic anhydride. I. Dimensional stabilisation. Plolzforschung, 52(4), 427 33. 

Fig. 13. Idealized structure of the product of hydroxyl/stearic ester functionalized hyperbranched polyesteramides based on adipic acid and diisopro-panolamine functionalized with octenyl succinic anhydride... 

It is Hkely that the diene also remains coordinated during the hydrosilylation reactions of phenylacetylene with HSiEts, catalyzed by [Ir(diene)(NCMe)(PR3)]BF4 complexes [PR3 = P Pr3, PMe3 diene = 1,5-cyclo-octadiene, tetraflorobenzobarre-lene (TFB)]. However, detailed studies on the [Ir(COD)(NCMe)(PMe3)]BF4 complex show that cyclo-octadiene carmot be considered, in this case, as an ideal innocent Hgand because it transform into complexes containing cyclo-octadiene, cyclo-octadienyl or cyclo-octenyl Hgands in a variety of coordination modes, due to an... 

T)-2-octenyl acetate was identified from the volatiles produced by the adult female predatory bug, Geocorispunctipes that attracted male bugs. This compound comprised a significant portion of female volatiles. Other components in the extracts from adults of both sexes included (T )-2-hexenyl acetate, ( )-2-octenal and several saturated hydrocarbons but were not part of the attractant. Homogenized adults also yielded (T )-2-hexenal and (T)-4-oxo-2-hexenal whereas cast skins from late instar nymphs contained (T)-2-octenal, (T)-4-oxo-2-octenal, (T)-2-octenoic acid, and other saturated hydrocarbons. ... 

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