Alkenes reaction with acetic anhydride

The decarbonylation-dehydration of the fatty acid 887 catalyzed by PdCl2(Ph3P)2 fO.Ol mol%) was carried out by heating its mixture with acetic-anhydride at 250 C to afford the terminal alkene 888 with high selectivity and high catalyst turnover number (12 370). The reaction may proceed by the oxidative addition of Pd to the mixed anhydride[755]. 

Ion 21 can either lose a proton or combine with chloride ion. If it loses a proton, the product is an unsaturated ketone the mechanism is similar to the tetrahedral mechanism of Chapter 10, but with the charges reversed. If it combines with chloride, the product is a 3-halo ketone, which can be isolated, so that the result is addition to the double bond (see 15-45). On the other hand, the p-halo ketone may, under the conditions of the reaction, lose HCl to give the unsaturated ketone, this time by an addition-elimination mechanism. In the case of unsymmetrical alkenes, the attacking ion prefers the position at which there are more hydrogens, following Markovnikov s rule (p. 984). Anhydrides and carboxylic acids (the latter with a proton acid such as anhydrous HF, H2SO4, or polyphosphoric acid as a catalyst) are sometimes used instead of acyl halides. With some substrates and catalysts double-bond migrations are occasionally encountered so that, for example, when 1 -methylcyclohexene was acylated with acetic anhydride and zinc chloride, the major product was 6-acetyl-1-methylcyclohexene. ... 

Finally, Thiele acetoxylation of quinones, by treatment with acetic anhydride and sulfuric acid, is another excellent method of introducing functionality at an alkene carbon atom, for further synthetic elaboration (equation 50)196. This reaction was recently used as a key synthetic step in the total synthesis of metachromin-A, a useful sesquiterpene quinone moiety197. 

The first step in this multistage reaction is the nucleophilic addition of sulfone anion 28 to aldehyde 8 (Scheme 14.6). This produces a p-alkoxysulfone intermediate 29 which is trapped with acetic anhydride. The resulting P acetoxysulfone mixture 22 is then subjected to a reductive elimination with Na/Hg amalgam to obtain alkene 23. The tendency of Julia-Lythgoe-Kocienski olefinations to provide ( )-1,2-disubstituted alkenes can be rationalised if one assumes that an a-acyloxy anion is formed in the reduction step, and that this anion is sufficiently long-lived to allow the lowest energy conformation to be adopted. Clearly, this will... 

A study carried out by Kocienski and Lythgoe flrst demonstrated the trans selectivity of the Julia coupling process. The authors found the i uctive elimination could best be carried out with the acet-oxy or benzoyloxy sulfones. If the lithio sulfone derivative is used for addition to the carbonyl, the reaction can be worked up with acetic anhydride or benzoyl chloride to obtain the alkene precursor. In cases where enolization of the carbonyl is a complication, the magnesium derivative can frequently be used successfully. A modification of the reductive elimination was found to be most effective. Methanol, ethyl acetate/methanol or THF/methanol were the solvents of choice and a temperature of -20 C was effective at suppressing the undesired elimination of the acetoxy group to produce the vinyl sulfone. With these modifications of the original procedure, the ability of the reaction to produce dienes as well as rran.r-disubstituted alkenes was demonstrated, llie diastereoisomeric erythro- and threo-acetoxy sulfones could be separated and it was demonstrated that both isomers were converted to the rrans-alkene. It... 

Among various microporous adsorbents such as alumina, sihca, clays, molecular sieves, etc., the HY zeolite was found to be best at promoting the acylation of 2,3-dimethyl-2-butene with acetic anhydride. The influence of numerous experimental parameters on the course of the reaction was investigated. Variations in the silica/alumina ratio of the zeolite, or in the relative proportions of reagents and catalyst, markedly affected the yield of 3,3,4-trimethyl-4-penten-2-one, whereas the reaction time and temperature were less influential. The procedure was extended to various other alkenes and it was possible to regenerate and to reuse the solid catalyst without significant loss of activity. 

Alkenes are also readily formed by dehydration ofhydroxybis(thienyl)alkanes (see Section IV). One reaction of particular interest is the formation of the acetylated alkenes 80a and 80b on treatment of the carbinol 78 with acetic anhydride-zinc chloride110 a possible mechanism involves the mixed anhydride 79 (Eq. 25). 

Epoxidation reactions have been successfully carried out using UHP as a source of hydrogen peroxide, provided that the reaction conditions and the acid anhydride are chosen carefully. Heaney and coworkers have demonstrated that nucleophilic alkenes can be converted to the corresponding epoxides using UHP with acetic anhydride and disodium hydrogen phosphate at room temperature as illustrated below. 

When terf-pentyl alcohol was reacted with acetic anhydride and perchloric or tetrafluoroboric acids, the reaction proceeded via the more stable trisubstituted alkene (21) under thermodynamic control and the reaction product was mainly a 2,3,4,6-tetramethylpyrylium salt (25). However, with terf-pentyl chloride, acetyl chloride and aluminum chloride or antimony pentachloride, the diacetylation occurred under kinetic control the alkene equilibration proceeds very fast with these Lewis acids so that the product (26) is derived from the more reaetive but less stable disubstituted alkene (22) 63,64 formulas below, the intermediate monoaeetylation products... 

Another amino acid synthesis is called the azlactone synthesis. Remember from before that an azlactone is an oxazolone (see 95). When glycine (52) is converted to its AT-benzoyl derivative (112 known as hippuric acid) by reaction with benzoyl chloride, treatment with acetic anhydride (AC2O) gives the azlactone 113. This is the reaction presented in the preceding section (see compormd 95). Compound 110 has the common name of hippuric acid azlactone. As with the thiohydantoin, the -CH2- unit in 113 is susceptible to an enolate anion condensation reaction with aldehydes (Chapter 22, Section 22.7.2), and reaction with 2-methylpropanal in the presence of pyridine gives azlactone 114. Catalytic hydrogenation of the alkene unit (Chapter 19, Section 19.3.2) and acid hydrolysis lead to the amino acid leucine (55). 

Alkylation Reactions. DMF dialkyl acetals undergo a variety of reactions with 1,2-diols. For example, the reaction of trans-cyclohexane-l,2-diol with DMF dimethyl acetal leads to the formation of cyclohexane epoxide (eq 2) with inversion of configuration. Similarly, wej 0-l,2-diphenyl-l,2-ethanediol gives trans-stilbene epoxide stereospecifically (eq 3). This method has also been applied in the synthesis of cholestane epoxide from vicinal diols. If the intermediate 2-dimethylamino-1,3-dioxolane is treated with Acetic Anhydride, reductive elimination to the alkene occurs with retention of stereochemistry (eq 4). " ... 

When acetic anhydride is used in the CF3CCI3 and zinc reaction with aldehydes, the initial addition product undergoes an elimination reaction to give 2-chloro-l,l,l-trifluoro-2-alkenes exclusively [60, 63] (equation 51)... 

Electrophilic addition reactions of tetravalent tellurium compounds have been reviewed.64 2-Naph-thyltellurium trichloride (ArTeCb) adds to alkenes in an anti stereospecific manner (equation 11), whereas tellurium tetrachloride gives mixtures of 2 1 adducts with both syn and anti addition.72 A one-pot alkene inversion procedure has been developed, based upon TeCU addition to alkenes followed by treatment of the (3-chloroalkyltellurium trichloride adduct with aqueous Na2S (Scheme 37).73 Tellurium compounds such as tellurinyl acetates, ArTe(0)0Ac, prepared in situ through reaction of tellurinic acid anhydrides with acetic acid, can be employed in oxytelluration and aminotelluration procedures (Schemes 38 and 39).74 In the oxytelluration reaction intermediate triacetates of the type RCH2Te(OAc)2Ph are reduced with hydrazine to the corresponding tellurides. 

The key butenolide needed by Buszek, for his synthesis of (—)-octalactin A, had already been prepared by Godefroi and Chittenden and coworkers some years earlier (Scheme 13.4).9 Their pathway to 10 provides it in excellent overall yield, in three straightforward steps from l-ascorbic acid. The first step entails stereospecific hydrogenation of the double bond to obtain L-gulono-1,4-lactone 13. Reduction occurs exclusively from the sterically less-encumbered ot face of the alkene in this reaction. Tetraol 13 was then converted to the 2,6-dibromide 14 with HBr and acetic anhydride in acetic acid. Selective dehalogenation of 14 with sodium bisulfite finally procured 10. It is likely that the electron-withdrawing effect of the carbonyl in 14 preferentially weakens the adjacent C—Br bond, making this halide more susceptible to reductive elimination under these reaction conditions. 

Cobalt complexes derived from Schiff bases 388 catalyzed the hydroxyacylation of electron-deficient alkenes (Fig. 90) [431, 432]. Thus, methyl acrylate 387 reacted with aliphatic aldehydes 386 in the presence of 5 mol% of the in situ generated catalyst, molecular oxygen, and acetic anhydride to 2-acyloxy-4-oxoesters 389 in 56-77% yield. When acetic anhydride was omitted, the yields of products were lower and mixtures of the free hydroxy compounds and acylated compounds resulting from Tishchenko reactions were obtained. Electron-rich alkenes did not undergo the transformation, since the addition of the acyl radical is much slower. The acylcobalt species inserts oxygen instead and acts as an epoxidation catalyst. 

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