4-PHENYL-6-HEPTEN

Titanium(IV) is a powerful but selective Lewis acid which can promote the coupling of allylsilanes with carbonyl compounds and derivatives In the presence of titanium tetrachlonde, benzalacetone reacts with allyltnmethylsilane by 1,4-addition to give 4-PHENYL-6-HEPTEN-2-ONE. Similarly, the enol silyl ether of cyclopentanone is coupled with f-pentyl chloride using titanium tetrachlonde to give 2-(tert-PENTYL)CYCLOPENTANONE, an example of a-tert-alkylation of ketones. 

CONJUGATE ALLYLATION OF a,g-UNSATURATED KETONES WITH ALLYLSILANES 4-PHENYL-6-HEPTEN-2-0NE (6-Hepten-2-one, 4-phenyl-)... 

Sakurai, H., Hosomi, A., Hayashi, J. Conjugate allylation of a,p-unsaturated ketones with allylsilanes 4-phenyl-6-hepten-2-one (6-hepten-2-... 

Abbreviations aapy, 2-acetamidopyridine Aik, alkyl AN, acetoniuile Ar, aryl Bu, butyl cod, 1,5-cyclooctadiene COE, cyclooctene COT, cyclooctatetraene Cp, cyclopentadienyl Cp , penta-methylcyclopentadienyl Cy, cyclohexyl DME, 1,2-dimethoxyethane DME, dimethylformamide DMSO, dimethyl sulfoxide dmpe, dimethylphosphinoethane dppe, diphenylphosphinoethane dppm, diphenylphosphinomethane dppp, diphenylphosphinopropane Et, ethyl Ec, feirocenyl ind, inda-zolyl Me, methyl Mes, mesitylene nb, norbomene orbicyclo[2.2.1]heptene nbd, 2,5-norbomadiene OTf, uiflate Ph, phenyl PPN, bis(triphenylphosphoranylidene)ammonium Pi , propyl py, pyridine pz, pyrazolate pz, substituted pyi azolate pz , 3,5-dimethylpyrazolate quin, quinolin-8-olate solv, solvent tfb, teti afluorobenzobaiTelene THE, tetrahydrofuran THT, tetrahydrothiophene tmeda, teti amethylethylenediamine Tol, tolyl Tp, HB(C3H3N2)3 Tp , HB(3,5-Me2C3HN2)3 Tp, substituted hydrotiis(pyrazol-l-yl)borate Ts, tosyl tz, 1,2,4-triazolate Vin, vinyl. 

Phenyl-V-heptene Typical Procedure for the Reaction of RCu BE, with Allylic Halides and Allylic Alcohols 11 ... 

The lithium enolates of cyclopentanone and cyclohexanone undergo addition-elimination to the 2,2-dimethylpropanoic acid ester of ( )-2-nitro-2-hepten-l-ol to give 2-(l-butyl-2-nitro-2-propenyl)cycloalkanones with modest diastereoselection. An analogous reaction of the enolate ion of cyclohexanone with the 2,2-dimethylpropanoic acid ester of (Z)-2-nitro-3-phenyl-2-propenol to give 2-(2-nitro-l-phenyl-2-propenyl)cyclohexanones was also reported. The relative configuration of these products was not however determined6. 

Phenyl-bicyclo[2.2.1]hepten-(2) liefert unter Angriff des Hydrids von deraro-Seite her das endo-2-Phenyl-bicyclo[2.2.1Yieptanl ... 

Because aldrin contains the bicyclo-(2.2.1)-heptene ring structure, it reacts typically with phenyl azide to form a phenyldihydrotriazole derivative. This reaction is of importance in that it provides the basis for an analytical method for determining aldrin (discussed more fully in 2). 

One mole of isoprene reacted with one mole of acetoacetate by using a bidentate phosphine as ligand (56). Reaction of 2,3-dimethylbutadiene with acetoacetate was carried out by using PdCl2 in the presence of sodium phenoxide. When PPh3 was used, a 1 2 adduct was obtained. On the other hand, use of P-phenyl-l-phospha-3-methyl-3-cyclopentene (105) at 100°C caused the 1 1 addition to give 3-carbomethoxy-5,6-dimethyl-5-hepten-2-one (106), from which 5,6-dimethyl-5-hepten-2-one (107) was formed. This compound is the useful intermediate for a-irone synthesis (96). 

Figure 1.13 Functional Monomers Used for Monolith Grafting 7-Oxabicyclo[2.2.1]hept-5-ene-2-carboxylic acid (I), 7-Oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride (II), and N-Phenyl-7-oxabicyclo[2.2.1]5-heptene-2,3-dicarboximide (III)...

Several Himple alkyl- and phenyl-substituted ethylene oxides have wen prepared in good yield by this procedure (Eq. 296). These include l-heptene oxide, 41 1-octene oxide,161 1-hexadeoone oxide, 46 cyclo-licxylothylene oxide,240 1,2-epoxy-4-phenylbutane,1 40 and 1,2-epoxy-J -pi icnylpr opane. 40>1BSo- . ws ... 

The hydroformylation of several olefins in the presence of Co2(CO)8 under high carbon monoxide pressure is reported. (S)-5-Methylheptanal (75%) and (S)-3-ethylhexanal (4.8%) were products from (- -)(S)-4-methyl-2-hexene with optical yields of 94 and 72%, respectively. The main products from ( -)(8)-2,2,5-trimethyl-3-heptene were (S)-3-ethyl-6,6-di-methylheptanal (56.6%) and (R)-4,7,7-trimethyloctanal (41.2%) obtained with optical yields of 74 and 62%, respectively. (R)(S)-3-Ethyl-6,6-dimethylheptanal (3.5% ) and (R)(S)-4,7,7-trimethyloctanal (93.5%) were formed from (R)(S)-3,6,6-trimethyl-l-heptene. (+/S)-l-Phenyl-3-methyl-1-pentene, under oxo conditions, was almost completely hydrogenated to (- -)(S)-l-phenyl-3-methylpentane with 100% optical yield. 3-(Methyl-d3)-l-butene-4-d3 gave 4-(methyl-d3)pentarwl-5-d3 (92%), 2-methyl-3-(methyl-d3)-butanal-4-d3 (3.7%), 3-(methyl-d3)pentanal-2-d2,3-d1 (4.3%) with practically 100% retention of deuterium. The reaction mechanism is discussed on the basis of these results. 

S)-l-Phenyl-3-methyl-l-pentene, initially synthesized to extend the data obtained with (+)(S)-2,2,5-trimethyl-3-heptene, under usual oxo conditions is almost completely hydrogenated with an optical yield of practically 100% while the hydroformylation products are barely detectable. 

Epoxidation of (Z)-2-methyl-2-hepten-l-ol gave epoxy alcohol 61 (80% yield, 89% ee) [2], of (Z)-2-methyl-4-phenyl-2-buten-l-ol gave 62 (90%, 91% ee) 177], and of (2T)-1 -hydroxy squalene gave 63 (93%, 78% ee) [85]. The epoxy alcohol 64 had >95% ee after recrystallization [91], In the epoxidation of (Z)-2-r-butyl-2-buten-l-ol, the allylic alcohol with a C-2 r-butyl group, the epoxy alcohol was obtained in 43% yield and with 60% ee [38], These results lead one to expect that other 2,3Z-disubstituted allylic alcohols will be epoxidized in good yield and with enantioselectivity similar to that observed for the 3Z-monosubstituted allylic alcohols (i.e., 80-95% ee). 

The results of the hydroformylation of internal olefins are reported in Table 9. In the case of (Z)- and (E)-2-butene, the same fare of the unsaturated carbon atom is formylated with either a rhodium- or platinum (—)-DIOP-containing catalytic system. With the rhodium catalyst, when an acyclic olefin is used as the substrate, the same fare is always attacked, and it is only the notation but not the geometric requirement that is different for (E)-l-phenyl-1-propene. The only exception is represented by bicyclo[2,2,l]heptene. However, using (—)-CHIRAPHOS instead of (—)-DIOP, also bieyelo[2,2,l]heptene behaves like internal butenes. No regularity is observed for the cobalt or ruthenium (—)-DIOP catalytic systems. With the same system, only in 3 cases out of 15 the face of the prochiral atom preferentially formylated has different geometric requirements. 

Male moths and butterflies have proven to be an especially rich source of interesting natural products. The sex pheromone produced in the wing glands of the lesser waxmoth, Achroia grisella, is composed of n-undecanal and (Zj-ll-octadecenal (98), whereas that of the greater waxmoth also contains n-undecanal (.99) but is dominated by n-nonanal (100). The scent brushes of male noctuid moths produce large amounts of aromatic compounds and terpenes which are believed to function as aphrodisiacs (101). Benzaldehyde, 2-phenyl ethanol, benzyl alcohol, 6-methyl-5-hepten-2-one, pinocarvone, and isobutyric acid have been identified in the secretions of different noctuid species (102), and it appears that these pheromones may possess some chemotaxonomic value. 

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