Bond-forming initiation

The radical polymerization behavior of captodative olefins such as acrylonitriles, acrylates, and acrylamides a-substituted by an electron-donating substituent is reviewed, including the initiated and spontaneous radical homo- and copolymerizations and the radical polymerizations in the presence of Lewis acids. The formation of low-molecular weight products under some experimental conditions is also reviewed. The reactivity of these olefins is analyzed in the context of the captodative theory. In spite of the unusual stabilization of the captodative radical, the reactivity pattern of these olefins in polymerization does not differ significantly from the pattern observed for other 1,1-disubstituted olefins. Classical explanations such as steric effects and aggregation of monomers are sufficient to rationalize the observations described in the literature. The spontaneous polymerization of acrylates a-substituted by an ether, a thioether, or an acylamido group can be rationalized by the Bond-Forming Initiation theory. 

The Bond-Forming Initiation Theory for Spontaneous Polymerizations 92... 

Application of Bond-Forming Initiation Theory to the Spontaneous... 

It is the purpose of this paper to review the implications of this unusual stabilization for the radical polymerization of captodatively substituted olefins. Also, the possibility of producing 1,4-tetramethylene diradicals from these olefins opens an important new area for the spontaneous polymerization of olefins. The latter will be discussed in the context of the Bond-Forming Initiation Theory [9-10],... 

The Bond-Forming Initiation Theory was proposed to explain spontaneous charge-transfer polymerizations of vinyl monomers [9-10]. This theory will be applied to the spontaneous polymerizations of captodative olefins. 

The Bond-Forming Initiation theory (Scheme 1), originally proposed in 1983, extends the Huisgen hypothesis and proposes that these same tetramethylenes are the true initiators for the observed spontaneous polymerizations, and that this concept is valid for both ionic and radical polymerizations [9, 10]. The tetramethylenes offer a lower energy pathway for initiation than ion radicals. 

The Bond-Forming Initiation theory is based on the fact that cycloaddition and initiation of copolymerization compete in the reactions of donor and acceptor monomers. Experimental conditions played a great role in that dilute solutions favored cycloadditions, while high concentration favored polymerization. The main concept is that the intermediates in the cycloaddition reactions are also the initiators of the polymerization. 

The Bond-Forming Initiation Theory gives a good interpretation of the observed spontaneous polymerizations of captodative monomers. The tetramethylene diradicals already implicated as initiators in the thermal (spontaneous) polymerizations of vinyl monomers can be particularly stabilized by captodative substituents. For comparison, and to initiate the polymerization of third monomers, captodative cyclobutanes and cyclopropanes are particularly appropriate precursors for generating tetra- and trimethylene diradicals. In particular the extensive work of Viehe [3,45,46] showed that thermolysis of captodative substituted cyclopropanes leads to trimethylene captodative diradicals at reasonable temperatures. Their initiating abilities for polymerization have not yet been determined. 

The mpture of hydrogen bonds formed initially between ester (PHB) and hydroxyl (PVA) or between two hydroxyl groups as the effective crosslinks promotes swelling in the blends, and as consequence an increase of both water diffiisivity and water equilibrium sorption. The third range of permeability curves can be recognized due to the inflection point observed for all samples containing PHB. It seems likely that to this moment the stmctural relaxation is completed and the water transport proceeds in accordance with regular diffusion mechanism. " ... 

The oxidation of the cyclic enol ether 93 in MeOH affords the methyl ester 95 by hydrolysis of the ketene acetal 94 formed initially by regioselective attack of the methoxy group at the anomeric carbon, rather than the a-alkoxy ketone[35]. Similarly, the double bond of the furan part in khellin (96) is converted ino the ester 98 via the ketene acetal 97[l23],... 

The mechanism of free radical polymerization of ethylene is outlined m Figure 6 17 Dissociation of a peroxide initiates the process m step 1 The resulting per oxy radical adds to the carbon-carbon double bond m step 2 giving a new radical which then adds to a second molecule of ethylene m step 3 The carbon-carbon bond forming process m step 3 can be repeated thousands of times to give long carbon chains... 

The extent of decarboxylation primarily depends on temperature, pressure, and the stabihty of the incipient R- radical. The more stable the R- radical, the faster and more extensive the decarboxylation. With many diacyl peroxides, decarboxylation and oxygen—oxygen bond scission occur simultaneously in the transition state. Acyloxy radicals are known to form initially only from diacetyl peroxide and from dibenzoyl peroxides (because of the relative instabihties of the corresponding methyl and phenyl radicals formed upon decarboxylation). Diacyl peroxides derived from non-a-branched carboxyhc acids, eg, dilauroyl peroxide, may also initially form acyloxy radical pairs however, these acyloxy radicals decarboxylate very rapidly and the initiating radicals are expected to be alkyl radicals. Diacyl peroxides are also susceptible to induced decompositions ... 

The addition of halogenated aliphatics to carbon-carbon double bonds is the most useful type of carbon-carbon bond forming synthetic method for highly halogenated substrates Numerous synthetic procedures have been developed for these types of reactions, particularly for the addition of perfluoroalkyl iodides to alkenes using thermal or photolytic initiators of free radical reactions such as organic peroxides and azo compounds [/]... 

The Corey-Winter reaction provides a useful method for the preparation of olefins that are not accessible by other routes. For instance it may be used for the synthesis of sterically crowded targets, since the initial attack of phosphorus at the sulfur takes place quite distantly from sterically demanding groups that might be present in the substrate molecule. Moreover the required vicinal diols are easily accessible, e.g. by the carbon-carbon bond forming acyloin ester condensation followed by a reductive step. By such a route the twistene 10 has been synthesized ... 

Perhalogenoaryls are more stable than the unsubstituted phenyls [176] and can be synthesized conveniently by oxidation of gold(I) complexes (demonstrating the stability of the Au-C bond). The initial product of oxidation addition seems to be the frans-isomer, which generally rearranges to the m-form ... 

Initiation is defined as the series of reactions that commences with generation of primary radicals and culminates in addition to the carbon-carbon double bond of the monomer so as to form initiating radicals (Scheme 3.1... 

The (TMS)3Si radical addition to terminal alkenes or alkynes, followed by radical cyclization to oxime ethers, were also studied (Reaction 50). The radical reactions proceeded effectively by the use of triethylborane as a radical initiator to provide the functionalized pyrrolidines via a carbon-carbon bond-forming process. Yields of 79 and 63% are obtained for oxime ethers connected with an olefin or propargyl group, respectively. 

In many eliminations to form C=0 and C=N bonds the initial step is loss of a positive group (normally a proton) from the oxygen or nitrogen. These may also be regarded as ElcB processes. 

Figure 7-6. Mechanism for catalysis by an aspartic protease such as HIV protease. Curved arrows Indicate directions of electron movement. Aspartate X acts as a base to activate a water molecule by abstracting a proton. The activated water molecule attacks the peptide bond, forming a transient tetrahedral Intermediate. Aspartate Y acts as an acid to facilitate breakdown of the tetrahedral intermediate and release of the split products by donating a proton to the newly formed amino group. Subsequent shuttling of the proton on Asp X to Asp Y restores the protease to its initial state.

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