L-Decene

The sample of l-decene was obtained from the Aldrich Chemical Company and distilled before use. 

The first fraction (bp 30-40 C) contains decenes which are formed by palladium-catalyzed isomerization of l-decene (indicated by a broad signal at 6 5.2-5.5 in the H NMR spectrum). 

A detailed analysis of the LAB isomer distribution in this experiment is provided in Table 1. The results are very similar for LAB production from benzene/l-decene mixtures using the same batch procedures and equipment (see also Table 1). 

The Michael reaction of nitromethane with methyl vinyl ketone and l-decene-3-one followed by reductive cyclization gives two isomeric pyrrolizidines, depending on reduction conditions (Eq. 10.74).117... 

Scheme 5. Reaction conditions i, reductive amination ii, protection of amino group iii, Collins reagent iv, Ph3F CHCioH2i" v, hydrolysis vi, Hg(OAc>2 vii, NaBH4 viii, l-decen-3-one ix, ethanedithiol x, Raney Ni xi, HCl-EtOH.

Cyclization by amidomercuration has been reported (391). Reaction of N-methoxycarbonyl-6-aminohept-l-ene (211) with mercuric acetate gave the organomercurial (212). Reductive coupling of 212 with l-decen-3-one in the usual way gave the cis and trans isomers (213). Successive treatment of 213 with ethanedithiol, Raney nickel, and ethanolic hydrogen chloride afforded ( )-sole-nopsin A (Id, 2 parts) and its isomer (Ic, 3 parts), which were separable by preparative gas chromatography (GC) (Scheme 5) (391). 

TABLE 9.21 Major Products Observed in the Particles Formed in the VOC - NO, Oxidations in Air of 1-Octene and l-Decene"... 

Possibly the most convincing evidence for positive ion-molecule reactions in polymers is the high rate of decay of vinyl unsaturation during the radiolysis of polyethylene, as recently discussed by Dole, Fallgatter, and Katsuura (13). The ideas of these authors with respect to the carbonium ion mechanism for vinyl decay by means of a dimerization reaction were largely suggested by the mechanisms proposed by Col-linson, Dainton, and Walker (5) for vinyl decay (polymerization) in the radiolysis of n-hexa-l-decene, Reactions 3 and 4 of Table I. 

Macro carbocyclic rings can be constructed by cyclization of nitrile oxides derived from oj-nitro-l-al-kenes (Scheme 22). If the intervening bridge is not longer than seven atoms, only fused bicyclic products are obtained. Thus, the nitrile oxide derived from nitro compound (75a) is cyclized in 44% yield to the 5,9-fused bicyclic isoxazoline (76a).38 10-Nitro-l-decene (75b) also cyclized to (76b) in unspecified yield.39 It should be noted that these results go counter to the usual regiochemistry of an intermolecular nitrile oxide cycloaddition where the five-substituted isoxazoline is usually,27 although not always,40 heavily preferred from reaction of a terminal alkene. Thus, geometric constraints have won out over the normal electronic control. 

A single dehydrobromination step occurs in the conversion of 1,2-dibromodecane to C10H19Br. Bromine may be lost from C-l to give 2-bromo-l-decene. 

Loss of bromine from C-2 gives ( > and (Z)-l-bromo-l-decene. 

Although the ylides are too unstable for isolation, they can be utilized in situ for stereoselective syntheses of a, j8-epoxy and -aziridinyl ketones. For example, the generation of l-phenyliodonium-l-decen-2-olate (45) in the presence of aliphatic and aromatic aldehydes affords the corresponding epoxy ketones with high trans-stereoselectivity (Scheme 73) [197]. Efforts to trap 45 with ketones were unsuccessful, leading instead to 10-eicosene-9,12-dione, the formal ylide dimerization product. 

The product of hydroboration is heated to convert it to its least sterically crowded isomer (Equation B3.5), and then l-decene is added. This sets up the overall elimination/readdition equilibrium shown in Equation B3.6 from which the more volatile product alkene is distilled. 

The cross-coupling of allylsilanes with alkenes [50] and styrene [58] also occurs via their preliminary isomerization followed by the reaction of 1-propenylsilane with exemplary olefin-l-decene resulting in l-(triethoxysilyl)-1-decene as a product (Eq. 31). If the cross-coupling takes place, an expected product of this reaction is l-silyl-2-undecene, which is not detected. 

The oxyamination of ( )-l-deuterio-l-decene was >95% diastereoselective. but not re-gioselective61. Complete regioselectivity was, however, observed on (E)-l-phcnyl-l-propene and 3-aryloxy-l-propene, from which l-(aryloxy)-2-hydroxypropanamides, a class of biologically active substances with -adrenergic receptor blocking effects, were obtained62. Limited reactivity of internal alkenes, especially (Z)-alkenes, was observed. Finally, phenol can be used instead of acetic acid. 

The stereochemistry of the cyclohexene adduct was established as cis by comparison of the product with the authentic tnms-isomcr prepared by ring opening of cyclohexene oxide with tert-butylamine. Similarly, the products obtained from (Z)- and ( )-l-deuterio-l-decene were converted to diastereomeric oxazolidinones which were compared with the authentic diastereo-mers. Furthermore, different diastereomers were obtained from ( )- and (Z)-l-phenylpropene, It is therefore reasonable to assume complete syn addition for all alkenes. 

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