Allyl cyanoacetate

The allyl cyanoacetate 731 can be converted into an a, /3-unsaturated nitrile by the decarboxylation-elimination reaction[460], but allyl malonates cannot be converted into unsaturated esters, the protonation and allylation products being formed instead. 

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... 

The preparation of malonic acid monoesters has been demonstrated using the microbial nitrilase activity of Corynebacterium nitrilophilus ATCC 21 419, Gordona terrae MA-1, or Rhodococcus rhodochrous ATCC 33 025 to hydrolyze methyl cyanoacetate, ethyl cyanoace-tate, M-propyl cyanoacetate, isopropyl cyanoacetate, M-butyl cyanoacetate, tertbutyl cyanoacetate, 2-ethylhexyl cyanoacetate, allyl cyanoacetate, and benzyl cyanoacetate [96]. By maintaining the concentration of nitrile in a reaction mixture at <5 wt%, significant inactivation of the nitrilase activity was avoided for example, a total of 25 g of M-propyl cyanoacetate was added in sequential 5g portions to a lOOmL suspension of Rhodococcus rhodochrous ATCC 33 025 cells (OD630 = 5.6) in 50 mM phosphate buffer (pH 7.0) over 30h at 25 °C to produce mono-M-propyl malonate in 100% yield (Figure 8.17). 

Allyl cyanoacetate (cyanoacetic acid allyl ester, cyanoacetic acid 2- propenyl ester) [13361-32-5]... 

Diethyl allylmalenate, allyl acetoacetate and allyl cyanoacetate do not give cyclic ketones, but migration of the double bonds and hydrogenation by hydrogen transfer take place [669]. 

Geranyl acetoacetate (685) is converted into geranylacetone (686). On the other hand, a mixture of E- and Z-isomers of 688 is obtained from neryl acetoacetate (687). The decarboxylation and allylation of the allyl malonate or cyanoacetate 689 affords the o-allylated acetate or nitriie[447]. The trifluoromethyl ketone 691 is prepared from cinnamyl 4.4,4-trifluoroacetoace-tate (690)[448],... 

The decarboxylation of allyl /3-keto carboxylates generates 7r-allylpalladium enolates. Aldol condensation and Michael addition are typical reactions for metal enolates. Actually Pd enolates undergo intramolecular aldol condensation and Michael addition. When an aldehyde group is present in the allyl fi-keto ester 738, intramolecular aldol condensation takes place yielding the cyclic aldol 739 as a main product[463]. At the same time, the diketone 740 is formed as a minor product by /3-eIimination. This is Pd-catalyzed aldol condensation under neutral conditions. The reaction proceeds even in the presence of water, showing that the Pd enolate is not decomposed with water. The spiro-aldol 742 is obtained from 741. Allyl acetates with other EWGs such as allyl malonate, cyanoacetate 743, and sulfonylacetate undergo similar aldol-type cycliza-tions[464]. 

The carbanion derived from dimethyl malonate reacts with the cyclic nitro compounds 422 of ring size 5, 6, 7, 8 and 12 to afford the corresponding esters 423. Acyclic allylic nitro compounds 424 (R = Me, CH2OAC or CC Et) are attacked by bulky nucleophiles, such as dimethyl malonate anion, mainly at the terminal primary carbon atom to give rearranged products 425, whereas smaller nucleophiles, e.g. the anion derived from methyl cyanoacetate, react at the tertiary carbon atom to yield 426409a 453 455. 

Another type of Cinchona alkaloid catalyzed reactions that employs azodicarbo-xylates includes enantioselective allylic amination. Jprgensen [51-53] investigated the enantioselective electrophilic addition to aUyhc C-H bonds activated by a chiral Brpnsted base. Using Cinchona alkaloids, the first enantioselective, metal-free aUyhc amination was reported using alkylidene cyanoacetates with dialkyl azodi-carboxylates (Scheme 12). The product was further functionalized and used in subsequent tandem reactions to generate useful chiral building blocks (52, 53). Subsequent work was applied to other types of allylic nitriles in the addition to a,P-unsaturated aldehydes and P-substituted nitro-olefins (Scheme 13). 

The addition of allylic (or benzylic) zinc halides to alkylidenemalonates (105),lo2s-c alkylidene-cyanoacetates (106),l02d e alkylidenephosphonoacetates (108),84,1 alkylidene barbiturates102f and their ary-lidene analogs occurs exclusively in a 1,4-addition mode. However, the addition of allylic zinc halides to alkylidenemalonates (105) is temperature dependent at low temperatures (-15 C), the homoallylic ma-lonate (128) is obtained, while at higher temperatures (68 C) the isomeric 2-cyclopentenedicarboxylate esters (129) are obtained by a zinc halide promoted electrocyclic closure of the intermediate ester (127 Scheme 48).102 ... 

A mechanism has been proposed for the syn-S allylic substitution of a-cyanoacetals with alkyllithium reagents.14 The matched (9) and mismatched (11) substrates gave different products [98% (10) and 85% (12), respectively] when treated with lithium (g) di-f-butyl biphenylide (LiDBB) in THF at -78 °C as shown in Schemes 6 and 7. The spiroether effect is the controlling factor in determining the products. 

Scheme 2 shows Rapoport s synthesis [15]. The cinnamic acid derivative 3 prepared from m-methoxy benzaldehyde [20] was ethylated by diethyl sulfate to give ethyl cinnamate derivative 4, followed by Michael addition with ethyl cyanoacetate to afford compound 5. Compound 5 was converted to lactam 6 by the reduction of the cyano group and subsequent cyclization. Selective reduction of the lactam moiety of 6 was achieved by treatment with trimethy-loxonium fluorob orate followed by sodium borohydride reduction. Amine 8 was obtained by the reductive methylation of amine 7. Amine 8 was converted to compound 9 by methylene lactam rearrangement [21], followed by selenium dioxide oxidation to provide compound 10. Allylic rearrangement of compound 10 and subsequent hydrolysis gave compound 12. The construction of the decahydroisoquinoline structure began with compound 12,... 

A reaction similar to the Claisen rearrangement but involving the migration of an allyl group from one carbon atom to another has been discovered recently 23 for example, ethyl 1-cyclohexenylallylcyanoacetate (XIII) rearranges quantitatively in ten hours at 170° to ethyl (2-allyl-cydohexylidene)-cyanoacetate (XIV). 

Allyl and benzyl bromides react with a,/ -unsaturated nitriles in the presence of indium(i) iodide under sonication to produce the corresponding allylated and benzylated imines, involving exclusive addition of the allyl/benzyl group to the nitrile moiety (Equation (63)).273 The reaction of allylindium reagents with methyl cyanoacetates affords the corresponding allylation-enamination products (Equation (64)).27 l-Acyl-l,2-dihydropyridines are prepared by indium-mediated allylation of 1-acylpyridinium salts (Equation (65)).275 Quinoline and isoquinoline activated by... 

Addition of allylic organozinc reagents to alkylidene malonates (106, 107) and alkylidene cyanoacetates (107) has also been reported. 

The stereospecific conversion of cyclohexene into the corresponding amido selenide 54 is illustrated in Scheme 8. These amidoselenenylation reactions are commonly employed for the preparation of allylic and saturated amides by oxidative or reductive deselenenylation. Propionitrile, butyronitrile, benzonitrile and ethyl cyanoacetate may be used in place of acetonitrile. Styrene gave poor results and other electron-rich olefins such as 1-methylcyclohexene or 2,3-di-methylbut-2-ene did not give the amidoselenenylation products. The reaction can also be effected starting from the hydroxy- or methoxyselenenylation products of alkenes, in the presence of water and trifluoromethanesulfonic acid in this case the nitriles are used in stoichiometric amounts [48c]. This methodology was employed to prepare the amidoselenenylation products of styrene, 55, and of electron-rich olefins. It was necessary, however, to replace the phenyl-... 

The Jorgensen group also applied the parent cinchona alkaloids as catalysts to the aza-Michael addition of hydrazones 8 to cyclic enones 9 [4] and the asymmetric deconjugative Michael reaction of alkylidene cyanoacetates 10 with acrolein (11) [5], However, only a moderate level of enantioselectivity was obtained in both reactions (Scheme 9.4). Of note, for the deconjugative Michael reaction, the delocalized allylic anion 12 could be generated via the deprotonation of 10 by the cinchona base and might attack the electrophilic enal at either the a- or the y-position. However, in this study, only the a-adducts were produced. 

Active methylene compounds such as 1,3-diketones, 1,3-keto carboxylic esters, malononitrile, and ethyl cyanoacetate were alkylated by alkyl halides catalyzed by the ionic liquid [bmim][OH] under microwave irradiation. The alkyl halides included allyl, benzyl, methyl, and butyl bromides/iodides. The open-chain 1,3-ketones produced the monoalkylated products, whereas the cyclic diketones provided the dial-kylated products in one stroke. Malononitrile and ethyl cyanoacetate also furnished the dialkylated products (Fig. 12.24) [17]. 

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