Allyl 2- 2- ethyl

The reaction can be applied to allyl malonates. Alkylation of diallyl mal-onate (734) with bromoacetate and acetoxymethylation afford the mixed triester 735. Treatment of the tricster 735 with Pd catalyst affords allyl ethyl itaconate (736). In a similar way, a-methylene lactone and the lactam 737 can be prepared[462]. 

Hydrogenolysis of the diallyl alkylmalonate 757 with formic acid in boiling dioxane affords the monocarboxylic acid 758. Allyl ethyl malonates are converted into ethyl carboxylates[471]. The malonic allyl ester TV-allylimide 759 undergoes smooth deallylation in refluxing dioxane to give the simple imide 760(472]. The allyl cyanoacetate 761 undergoes smooth decarboxylation to give... 

There are also palladium-catalysed procedures for allylation. Ethyl 3-bromo-l-(4-methylphenylsulfonyl)indole-2-carboxylate is allylated at C3 upon reaction with allyl acetate and hexabutylditin[27], Ihe reaction presumably Involves a ir-allyl-Pd intermediate formed from the allyl acetate, oxidative addition, transmetallation and cross coupling. 

Peroxides. These are formed by aerial oxidation or by autoxidation of a wide range of organic compounds, including diethyl ether, allyl ethyl ether, allyl phenyl ether, dibenzyl ether, benzyl butyl ether, n-butyl ether, iso-butyl ether, r-butyl ether, dioxane, tetrahydrofuran, olefins, and aromatic and saturated aliphatic hydrocarbons. They accumulate during distillation and can detonate violently on evaporation or distillation when their concentration becomes high. If peroxides are likely to be present materials should be tested for peroxides before distillation (for tests see entry under "Ethers", in Chapter 2). Also, distillation should be discontinued when at least one quarter of the residue is left in the distilling flask. 

Enantioselectivity (which is hnked to the regioselectivity of the attack of the nucleophile to the coordinated allyl) in the allylic amination of 1,3-diphenyl-allyl ethyl carbonate was also very low compared to the P-N system. This was attributed to the comparable fran -influence of P and NHC functionalities, leading to poor regioselec-tion of the two aUyl termini trans to the P and NHC ligands by the nucleophile [95],... 

Generation and Reaction of Allyltitanium Reagents (Section 9.3) 2-(4-Bromophenyl)-l-phenyl-3-buten-l-ol [42] To a solution of l-(4-bromophenyl)allyl ethyl carbonate (285 mg, 1.0 mmol) and Ti(OiPr)4 (0.296 mL, 1.0 mmol) in diethyl ether (5 mL) was added iPrMgBr (1.20 m in diethyl ether, 2.0 mmol) at 50 °C. The resulting yellow solution was stirred at —50 to —40 °C for 1.5 h, in the course of which it became brown. Benzaldehyde (74.3 mg, 0.70 mmol) was then added at —40 °C and the mixture was allowed to warm to 0 °C over a period of 30 min. After the addition of aqueous 1 n HC1 (5 mL) at this temperature, the mixture was allowed to warm to ambient temperature. The organic layer was separated and the aqueous layer was extracted with diethyl ether (10 mL). The combined organic layers were washed with saturated aqueous NaHC03 solution (5 mL), dried over... 

Individually indexed compounds include f Allyl ethyl ether, 1955... 

The slow carbozincation, attributed to the presence of TMEDA, was more problematic when substrate-induced diastereoselection was also involved. Thus, addition of zincated allyl ethyl ether to the alkenyllithium derived from the secondary y-iodo allylic ether 209 afforded a 65/35 mixture of the diastereomers 228 and 229 in low yield after hydrolysis. The erosion of diastereoselectivity was not a consequence of a less efficient substrate-induced diastereoselection but rather of the fact that both the (E) and (Z) isomers of the zincated allyl ethyl ether had reacted. Although the use of a catalytic amount of TMEDA (10 mol%) in the metallation step substantially improved the yield, the diastereoselectivity remained low (equation 111)151. 

Nevertheless, chiral propargylic amines remain interesting substrates for achieving the diastereoselective addition of substituted allylic organozinc compounds to metallated alkynes. Besides crotylzincation, one example of diastereoselective addition of zincated allyl ethyl ether to 328 has also been reported183. 

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