Allyl bromide Aluminum iodide

When the metallic additive to the intermediate 374 was zinc dihalide (or another Lewis acid, such as aluminum trichloride, iron trichloride or boron trifluoride), a conjugate addition to electrophilic olefins affords 381 . In the case of the lithium-zinc transmetallation, a palladium-catalyzed Negishi cross-coupling reaction with aryl bromides or iodides allowed the preparation of arylated componnds 384 ° in 26-77% yield. In addition, a Sn2 allylation of the mentioned zinc intermediates with reagents of type R CH=CHCH(R )X (X = chlorine, bromine) gave the corresponding compounds 385 in 52-68% yield. ... 

This procedure is a modification of one described by Cortese.4 Allyl chloride is employed rather than allyl bromide because of its low cost. Biallyl has been prepared by the action of sodium 6 or aluminum 6 on allyl iodide from allyl mercuric iodide by dry distillation 7 or by the action of potassium cyanide solution 8 and by the action of magnesium on allyl bromide,4-9 on allyl chloride,4-10 on allyl iodide,11 or on 1,2,3-tribromopropane.12... 

In the presence of bismuth(lll) chloride-aluminum, allylic bromides have been found to react with aldehydes at room temperature in tetrahydrofuran-water to afford the corresponding homoallyhc alcohols in high yields (Wada et al, 1987). Water was found to play a crucial role since the allylation failed in pure tetrahydrofuran. Only a catalytic amount of bismuth chloride was needed to carry out the reaction. Bismuth(ill) chloride was reduced by aluminum to zero-valent bismuth, which could insert into the carbon-bromine bond of the allylic bromide to afford an allylbismuth intermediate as the reactive species. The allylation reaction could occur with the couple Bi(0)-Al(0) in tetrahydrofuran-water only in the presence of a catalytic amount of hydrobromic acid (Wada et al, 1990). Since bismuth(O) was postulated to be an intermediate oxidation state, the reaction was accomplished via an electrochemical redox pathway (Figure 4.1) in a two-phase system (Minato and Tsuji, 1988). Reactions mediated by Bi(0) as the only promotor were sluggish (Wada et ah, 1990). An exception was, however, reported with the coupling between p-nitrobenzaldehyde and allyl iodide in water (Chan and Isaac, 1996). 

The methods for making allyl alcohol are many. It may be prepared by (a) the action of metals upon dichlorohydrin 1 (b) the reduction of acrolein 2 (c) the action of potassium hydroxide on trimethylene bromide 3 (d) the catalytic decomposition of glycerol with aluminum oxide 4 (e) the hydrolysis of allyl iodide 5 (/) the decomposition of glycerol triformate 6 (g) the action of formic acid upon glycerin 7 and (h) the action of... 

ALKENES Allyl dimethyldithiocarbamate. Bis(t -cyclopentadienyl)niobium trihydride. Cyanogen bromide. Di-n-butylcopperlithium. a,o-Dichloromethyl methyl ether. 2,3-Dimethyl-2-butylborane. N,N-Dimethyl dichlorophosphoramide. Diphenyl diselenide. Di-n-propylcopperlithium. Ferric chloride. Grignard reagents. Iodine. Lithium phenylethynolate. Lithium 2,2,6,6-tetramethylpiperidide. Methyl iodide. o-Nitro-phenyl selenocyanate. Propargyl bromide. rra s-l-Propenyllithium. Selenium. Tetrakis(triphenylphosphine)palladium. Titanium(IH) chloride. Titanium trichloride-Lithium aluminum hydride. p-Toluenesulfonylhydrazine. Triphenylphosphine. Vinyl-copper reagents. Vinyllithium. Zinc. 

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