Acryloyl compounds

Reactive double bonds are capable of undergoing addition reactions with sulfhydryl groups. A popular example of this type of functional group is the maleimide group (Section 2.2). However, derivatives of acrylic acid are also able to participate in this reaction, although the rate of sulfhydryl addition is somewhat slower than that of maleimides. The reaction of an acryloyl compound with a sulfhydryl group occurs with the creation of a stable thioether bond (Reaction 18). 

Natural acryloyl compounds can also undergo CTI catalyzed by enzymatic systems. In this way, the CTI of maleylacetoacetate, a degradation product of phenylalanine and tyrosine, to fumarylacetoacetate was achieved by the cis-trans isomer-ase glutathione system. The reaction seems to involve a nucleophilic attack at the C2 carbon rather than a conjugated addition and the subsequent rotation of the single bond [58]. 

Urea has no promoting effect on the A AM polymerization initiated with Ce(lV) ion. Recently, Qiu et al. [24] have studied the effect of N-acryloyl-N -4-tolylurea (ATU), N-methacryloyl-N -4-tolylurea (MTU), and N-acetyl-N -4-tolylurea (AcTU) on A AM polymerization initiated with Ce(IV) ion and found that these three urea compounds have a high promoting effect on the polymerization of AAM. The data are cited in Table 4. 

It is interesting that cyclopropenone itself reacts with bromine at low temperatures giving a 1 I-compound of probable structure 314. On warming to 0 °C, 314 is converted to trans- 3-bromo acryloyl bromide (J75)197 ... 

However, most asymmetric 1,3-dipolar cycloaddition reactions of nitrile oxides with alkenes are carried out without Lewis acids as catalysts using either chiral alkenes or chiral auxiliary compounds (with achiral alkenes). Diverse chiral alkenes are in use, such as camphor-derived chiral N-acryloylhydrazide (195), C2-symmetric l,3-diacryloyl-2,2-dimethyl-4,5-diphenylimidazolidine, chiral 3-acryloyl-2,2-dimethyl-4-phenyloxazolidine (196, 197), sugar-based ethenyl ethers (198), acrylic esters (199, 200), C-bonded vinyl-substituted sugar (201), chirally modified vinylboronic ester derived from D-( + )-mannitol (202), (l/ )-menthyl vinyl ether (203), chiral derivatives of vinylacetic acid (204), ( )-l-ethoxy-3-fluoroalkyl-3-hydroxy-4-(4-methylphenylsulfinyl)but-1 -enes (205), enantiopure Y-oxygenated-a,P-unsaturated phenyl sulfones (206), chiral (a-oxyallyl)silanes (207), and (S )-but-3-ene-1,2-diol derivatives (208). As a chiral auxiliary, diisopropyl (i ,i )-tartrate (209, 210) has been very popular. 

Optically active 3-arylisoxazoline-5-carboxylic acid derivatives 403 or 404 have been, prepared by the reaction of (S)- or (/ )-3-acryloyl-4-benzyl-5,5-dimethyloxazolidin-2-one (405 or 406) with nitrile oxides, obtained from benzo-hydroximoyl chloride and its substituted derivatives in the presence of a catalytic amount of metal salt, for example, Yb(OTf)3 (445). This procedure improves the diastereoselectivity of compounds 403 or 404, which are industrially useful as intermediates for various drugs and agrochemicals. It also enables the amount... 

Compounds 3 (when R=He) and 5 are available In commercial quantities. Compound 4 may also be purchased or prepared In high yield via hydrogenation of 3 over a promoted Raney nickel catalyst (C. 6. Coe, unpublished results). The condensation of 4 with distilled acryloyl chloride proceeds In over 95X yield. 

Similar acryloyl imidazolidinones have been used for the asymmetric 1,4-addition of organomagnesium compounds in the presence of a Lewis acid. The diastereoselectivity is variable and was found to be highly depending on the nature of all substrates. ... 

Lewis acid-mediated addition of (phenylthio)trimethylsilane to acryloyl silane takes place to give l,3-bis(phenylthio)-l-trimethylsilylprop-l-ene (18). This compound may be deprotonated with t-butyl lithium at the /J-position and alkylated to give a range... 

A ruthenium-catalyzed three-component reaction between propargylic alcohols, 1,3-dicarbonyl compounds, and primary amines leading to fully substituted pyrroles was developed <07CEJ9973>. Cyclohexa[a]pyrroles ( azabicyclo[4.3.0] systems ) were formed by a three-component sequence involving allenic ketones, primary amines, and acryloyl chloride <07SL431>. An oxidative dimerization sequence involving arylpyruvates in the presence of ammonia was the key step in an approach to the pyrrole natural product, lukianol A <07S608>. 

Preparative Methods prepared by the reaction of (-)-8-Phenylmenthol, acryloyl chloride, Triethylamine, and 4-Dimethylaminopyridine in CH2CI2 at 0 °C. Following an aqueous workup, the compound is purified by chromatography on silica gel. ... 

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