2-Methoxyallyl bromide

Silver trifluoroacetate is used in a one step synthesis of bicyclo[3 2 2]nona-6,8-diene-3-one from 2-methoxyallyl bromide and benzene [50] (equation 23) Analogous reactions of toluene, p-xylene, and mesitylene yield the corre spending substituted bicyclo[3 2 2]noiia-6,8-diene-3-ones [50]... 

Metalation of the amidine 87, followed by introduction of 2-methoxyallyl bromide, furnished the intermediate 88, which underwent acid-induced cyclization to the product 89 (Scheme 12), illustrating an interesting approach to polyfunctionalized indoles suitable for further elaboration <20020L1819>. 

Methoxyallyl cation (5a Y = OMe), derived from 2-methoxyallyl bromide (4a X = Br, Y = OMe) and silver trifluoroacetate in the presence of sodium carbonate, reacts with benzene, toluene, p-xylene or mesitylene. 2-Ethoxyallyl alcohol (4c X = OH, Y = OEt) in the presence of trifluoroacetic anhydride generates the 2-ethoxyallyl cation (5c Y = OEt). 2-Ethoxyallyl alcohol (4c) is probably more advantageous than the corresponding 2-methoxyallylic species (4a Y = OMe) because dealkylation of the intermediary oxonium ion seems to be less facile, and the ethyl enol ether is more nucleophilic than the methyl enol ether. Treatment of cyclic a-chloroenamines (4f X = Cl, Y = morpholino) and (4g X = Cl,... 

Cychadditioas. Treatment of 2-methoxyallyl bromide with silver trifluoroacetale (1, 1018-1019) under carefully controlled conditions generates the 2-methoxyallyl cation (a), which undergoes cycloaddition with dienes. For example, the bromide in... 

CYCLOADDITIONS f-Butyicyanoketene. a-Chloro-N-cyclohexylpropanaldoxime. Chlorosulfonyl isocyanate. Dichloroke-tene. Dimethyl acetylenedicarboxylate. Diphenyl ketene, 2-Methoxyallyl bromide. 2-Methoxy-6-methyl-l,4,3,5-oxathiadia-zine 4,4-dioxide. Oxygen, singlet. 4-Phen-yl-l,2,4-triazoline-3,5-dione. Silver fluoro-borate. Trimethylsilyldiazomethane. 

Cycloaddition to arenes. Benzene reacts with the 2-methoxyallyl cation (a), formed from 2-methoxyallyl bromide by reaction with silver trifluoroace-tate, to give bicyclo[3.2.2]nona-6,8-diene-3-one (1) at room temperature (6% yield). Adducts are also obtained from p-xylene (3.5% yield) and toluene. The... 

CYDOADDITIONS Antimony(V) fluoride. Carbon disulfide. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone. Dimethyl acetylenedicarboxylate. Dimethylketene. Ethylaluminum dichloride. 2-Methoxyallyl bromide. Ninhydiin. Sodium cyclopentadienyldicarbonyl-ferrate. Sodium iodide-Coppet. Tetracyanoethylene. Tetramethylcyclobutadiene-Aluminum chloride complex. 

ACETONYLATION 2-Methoxyallyl bromide. w-(2-Methoxyallyl)nickel bromide. 

Methoxyallyl bromide monoalkylates acids, nitriles, esters, ketones, dialkyl-amides, enamines, and imines in 44—96% yield, e.g. alkylation of the lithium salt of imines followed by hydrolysis gives 1,4-diones (Scheme 21). ... 

Reaction of norbornadiene with diphenylketen slowly gives the expected exo [2 -f- 2] 1 1 adduct, but in the presence of excess diene and after longer times a low yield of (324) is produced. Brief heating at 200 °C converts (324) into (325).Benzene reacts with 2-methoxyallyl bromide in the presence of NajCOg and AgOCOCFj at room temperature to yield 11 % of (326). This is believed to be a concerted cycloaddition of the 2-methoxyallyl cation. ... 

Similarly, reaction of Grignard reagent 112 with 2-methoxyallyl bromide [75] leads to compound 113 that leads after acidic deprotection of the formamidine moiety and the enol ether to the indole cyclization product 114 in 90% yield (Scheme 4.25). 

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