F Allyl acetate

Acetohydrazide, 0912 Acetone oxime, 1258 Acetylenedicarboxylic acid, 1405 Acrylaldehyde, 1145 f Allyl acetate, 1912 A-Ally lthiourca. 1600 4-Aminophenylazobenzene, 3487 Ammonium dichromate, 4246 Ammonium peroxodisulfate, 4576 4-Azidobenzaldehyde, 2697 2-Azido-2-phenylpropane, 3159 f Aziridine, 0863 Azobenzene, 3483 Azoformamide, 0816 Azoisobutyronitrile, 3011 Azoxybenzene, 3485 Benzaldehyde oxime, 2760... 

Acetohydrazide, 0908 Acetone oxime, 1254 Acetylenedicarboxylic acid, 1401 f Acrylaldehyde, 1142 f Allyl acetate, 1906 iV-Allylthiourea, 1595 4-Aminophenylazobenzene, 3481 Ammonium dichromate, 4240 Ammonium peroxodisulfate, 4571 2-Azido-2-phenylpropane, 3154... 

The Pd(0)-catalyzed electrophilic reaction of allyl acetates (301) with elec-trochemically induced carbanions leading to (302) has been performed (Scheme 115) [436], The electrolysis is carried out in a DM F-Et4NCl04-(Pt) system in the presence of the active hydrogen compound, Ph3P, and Pd(II)(PhCN)2Cl2 at a current density of 0.26 A dm and the allyl acetate (301). 

Although the catalytic reactions described above involve mononuclear Rh and Rh complexes, dinuclear Rh compoimds have also been studied as catalyst precursors in oxygenation reactions. The system [Rh2(p.-OAc)4]/ f-BuOOH is effective in the oxidation of cyclic alkenes such as cyclopentene, cyclohexene and cycloheptene, mainly to o, /i-unsaturated ketones and allylic acetates, but with poor yields (Eq. 4) [30,31]. 

Carbamates are allylated in the presence of strong bases in DMSO or HMPA[197], Phthalimide (320) and succimide are allylated with the nllyl-isourea 321 at room temperature or the allylic acetate 322 at 100 [Pg.454]

Although an y.-C F group is known to retard, S 2 reactions of carbon nucleophiles with alkyl sulfonates, it has now been found that y-trifluoromethyl ated allylic acetals undergo, S 2 -typc reactions with Grignard reagents in presence of catalytic amounts of CuCN and TMS-C1 without formation of, S 2 products.110 This provides an alternative means of introducing a carbon nucleophile adjacent to a CF3 group. 

The synthesis of the bioactive natural product warburganal from (-)-sclareol was carried out by A.F. Barrero et al. The bicyclic allylic acetate was epoxidized and deacetylated under basic conditions. Next, the solution of the ketoepoxide in glacial acetic acid was treated with hydrazine hydrate and the resulting mixture was heated at reflux for 30 minutes to afford the bicyclic allylic did in excellent yield. 

Another interesting point is the regioselectivity of these [3+2]-cyeloadditions. Whenever a 2-substituted methylenecyclopentane is detected in a codimerization, catalyzed by a Pd(0) compound, the substitution pattern is the same as found in [3 -f 2]-cycloadditions starting with 2-[(trimethylsilyl)methyl]allyl acetates 183) (Eq. 85). 

Benzyltriethylammonium tetrathiomolybdate in CH3CN in 61-97% yield. Deprotection is compatible with esters such as benzyl, allyl, acetate, and f-butyl... 

Burke and Jiang reported that the palladium-catalyzed diastereoselective double allylation of the diol bis(allylic acetate) 613 using (R,R) DPPBA 607 afforded the bis-tetrahydrofuran core 614 in 97% yield (Scheme 187).265 The resulting diene 614 was further transformed into a known intermediate 615 for the synthesis of uvaricin. They demonstrated that palladium (0)-catalyzed desymmetrization of the C2 diol 616 with Trost s ligand 607 afforded the tetrahy-drofuran 617 diastereoselectively (Scheme 188).266 The product 617 was manipulated to the F ring of halichondrin B (618). 

Analogous allylic oxidations of higher olefins over heterogeneous palladium catalysts afford mixtures of products owing to the unsymmetrical nature of the f-allyl intermediate. For example, cis- or trans-2-butene gives a mixture of branched and linear allylic acetates. With olefins containing more than four carbon atoms palladium-catalyzed isomerization can lead to complex mixtures of products, which severely restricts the synthetic scope of these reactions. 

Claisen rearrangement of ally silyl ethers (4,307-308). Katzenellenbogen and Christy have extended the rearrangement of silyl enol ether derivatives of allylic acetates to y,S-unsaturated acids to systems in which a trisubstituted double bond is generated. Thus 3-acetoxy-2-methyl-l-nonene (1) was treated with lithium N-isopropylcyclohexylamide (LilCA) in THF at -78° and then with f-butyldimethylchlorosilane to give the f-butyldimethylsiloxyvinyl ether... 

As alluded to above, this version of the Jt-allyl palladium reaction uses an allylic acetate or chloride. The use of the acetate is more common because acetate is a much weaker nucleophile than chloride. When it involves a substrate where diastereomeric products can result, the stereochemistry of the nucleophilic displacement is an important issue. Palladium assisted alkylation proceeds with net retention of configuration of the acetate or chloride, as seen in the conversion of 375 to 376.223e,f... 

Some recent NMR studies on the copolymerization of allyl acetate with methyl methacrylate, butyl acrylate, and styrene reported their reactivity ratios (cf Table IXb) [65]. The reported error terms, if we assume them to be standard deviations, are quite large with respect to the ri term. Therefore it is problematic whether these numbers are really meaningful. It would seem to us that the large f-2 terms imply that substantially only homopolymers of these three vinyl monomers form. This situation is modified in the case of allyl methacrylate or allyl acrylate copolymers, as will be mentioned below. With these acrylic derivatives, copolymerization depends on the acrylic bonds primarily with modifications due to the allylic hydrogen. Subsequently, the allylic units in a copolymer of allyl methacrylate with butyl methacrylate, for example, will be the sites for crosslinking. 

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