Methyl acrylate generation

In the case of the template 204, the endo/exo selectivity was only 1.8 1, but the material yield was high with a facial selectivity of 10 1. The ylides were also trapped with methyl acrylate, generating the expected cycloadducts with reasonable regio and diastereocontrol. Although the endo/exo selectivity was relatively poor, the facial selectivity and material yield were both reasonable and the removal of the template is nondestructive. 

Treatment of A -benzyltnfluoroacetimidoyl chloride with triethylamine in toluene at room temperature leads to in situ generation of trifluoroacetonitrile ben-zylide [4J] (equation 43), which reacts with methyl acrylate to form cycloadducts [43] (equation 44) Although the kinetic ratio of products favors the cis adduct (3 1), thermodynamic equilibration leads to an excess of the trans isomer (7 1). 

The reaction of methyl acrylate and acrylonitrile with pentacarbonyl[(iV,iV -di-methylamino)methylene] chromium generates trisubstituted cyclopentanes through a formal [2S+2S+1C] cycloaddition reaction, where two molecules of the olefin and one molecule of the carbene complex have been incorporated into the structure of the cyclopentane [17b] (Scheme 73). The mechanism of this reaction implies a double insertion of two molecules of the olefin into the carbene complex followed by a reductive elimination. 

The cross metathesis of acrylic amides [71] and the self metathesis of two-electron-deficient alkenes [72] is possible using the precatalyst 56d. The performance of the three second-generation catalysts 56c,d (Table 3) and 71a (Scheme 16) in a domino RCM/CM of enynes and acrylates was recently compared by Grimaud et al. [73]. Enyne metathesis of 81 in the presence of methyl acrylate gives the desired product 82 only with phosphine-free 71a as a pre-... 

The cycloadducts formed from the Diels-Alder reaction of 3-amino-5-chloro-2(17/)-pyrazinones with methyl acrylate in toluene are subject to two alternative modes of ring transformation yielding either methyl 6-cyano-l,2-dihydro-2-oxo-4-pyridinecarboxylates or the corresponding 3-amino-6-cyano-l,2,5,6-tetrahydro-2-oxo-4-pyridinecarboxylates. From the latter compounds, 3-amino-2-pyridones can be generated through subsequent loss of HCN <96 JOC(61)304>. Synthesis of 3-spirocyclopropane-4-pyridone and furo[2,3-c]pyridine derivatives can be achieved by the thermal rearrangement of nitrone and nitrile oxide cycloadducts of bicyclopropylidene <96JCX (61)1665>. 

If chain transfer of the radical center to a previously formed polymer molecule is followed ultimately by termination through coupling with another similarly transferred center, the net result of these two processes is the combination of a pair of previously independent polymer molecules. T. G. Fox (private communication of results as yet unpublished) has suggested this mechanism as one which may give rise to network structures in the polymerization of monovinyl compounds. His preliminary analysis of kinetic data indicates that proliferous polymerization of methyl acrylate may be triggered by networks thus generated. 

Riant et al. in 2006 reported an enantioselective reductive aldol reaction of acetophenone and methyl acrylate mediated by PhSiH3 (140 mol %) and catalyzed by a complex generated in situ from [CuF(Ph3P)3]2MeOH (1-3 mol %) and a chiral bisphosphine (1-3 mol %) [57]. According to Mori s... 

The complex OsH(OH)(CO)(P Pr3)2 also reacts with methyl acrylate, methyl vinyl ketone, and allyl alcohol.91 Reaction with methyl acrylate leads to OsH(OH) (COXrf-CH2=CHC02MeXP Pr3)2 containing the olefin trans to the hydride ligand. In solution, this complex releases the olefin to generate the starting complex. The thermodynamic magnitudes involved in the equilibrium have been determined in toluene-t/a by 31P 1H NMR spectroscopy. The values reported are AH° = 17.0 0.5 kcal-mor1 and AS° = 54.0 1.2 cal-K 1-mol 1. In the presence of the methyl vinyl ketone complex OsH(OH)(CO)(P Pr3)2 affords 0sH CHCHC(0) Me (CO)(P Pr3)2 and water, whereas in the presence of allyl alcohol the loss of... 

Methyl acetoacetate, 24, 70 4-Methvl-7-acetoxycoumarin, 21, 24 Methyl acrylate, 20, 64, 81 Methylal, 20, 60 Methylaminc, 20, 36 anhydrous, 20, 35 35% aqueous solution, 21, 81 generator, 20, 35 hydrochloride, 21, 82 N-Methylaminoaromatic acids, 22, 93 Methyl amyl ketone, 23, 70 Methylaniline, 20, 11, 66 Methylation, 20, 97 Methyl c[-bromo-/3-methoxypropio nate, 20, 81... 

A number of examples have been reported documenting the use of palladium phosphine complexes as catalysts. The dialkyl species [PtL2R2] (L2 = dmpe, dppe, (PMe3)2 R = Me, CH2SiMe3) catalyze the reaction of [PhNH3]+ with activated alkenes (acrylonitrile, methyl acrylate, acrolein).176 Unfunctionalized alkenes prove unreactive. The reaction mechanism is believed to proceed via protonation of Pt-R by the ammonium salt (generating PhNH2 in turn) and the subsequent release of alkane to afford a vacant coordination site on the metal. Coordination of alkene then allows access into route A of the mechanism shown in Scheme 34. Protonation is also... 

In yet another example of an in situ reductive generation of an enolate, fi-amido esters are formed via the reaction of an o, /3-unsaturated ester with a silane in the presence of an isocyanate (Eq. 294).475 The yields obtained using methyl acrylate and methyl crotonate as substrates are generally excellent. 

Next, we examined the reduction of cation pools in the presence of radical acceptors. The radical that is formed by one-electron reduction of the cation is expected to add to a carbon-carbon double bond. The electrochemical reduction of 2 in the presence of methyl acrylate gave the expected addition product 16 (Scheme 9). A mechanism involving addition of radical 14 to the acrylate to generate radical 17 followed by subsequent reduction of anion 18, which is protonated to give 16 has been suggested. 

Figure 10. Composite Plot of Weight Loss versus Temperature (°C) for the Thermal Degradation of Vinylidene Chloride/ Methyl Acrylate (Five Mole Percent) Copolymers Generated Using Different Initiators.

The desired long spacer necessary to allow multiple branch construction, was obtained with commercial tetra(ethylene glycol) which was readily modified into aminoacetal 21 in five steps (Scheme 8). Using 21 as an amine source, poly(amidoamine) (PAMAM) dendrons were prepared according to published protocol using reiterative cycles of methyl acrylate and ethylenediamine reactions. The terminal amines of each generation (G = 1, G = 2 and G = 3, 22a-c) were obtained quantitatively from each of the half generation methyl ester precursors. 

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