Acylation, radical compounds

Radical-based carbonylation procedures can be advantageously mediated by (TMSlsSiH. Examples of three-component coupling reactions are given in Reactions (74) and (75). The cascade proceeds by the addition of an alkyl or vinyl radical onto carbon monoxide with formation of an acyl radical intermediate, which can further react with electron-deficient olefins to lead to the polyfunctionalized compounds. ... 

When applied to ketones, this is called Norrish Type / cleavage or often just Type I cleavage. In a secondary process, the acyl radical R —CO can then lose CO to give R radicals. Another example of a category 1 process is cleavage of CI2 to give two Cl atoms. Other bonds that are easily cleaved by photolysis are the 0—0 bonds of peroxy compounds and the C—N bonds of aliphatic azo compounds R—N=N—R. The latter is an important source of radicals R , since the other product is the very stable N2. 

Aldehydes are oxidized by dioxygen by the chain mechanism in reactions brought about in different ways initiated, thermal, photochemical, and induced by radiation as well as in the presence of transition metal compounds [4-8]. Oxidation chains are usually very long from 200 to 50,000 units [4], Acyl radicals add dioxygen very rapidly with a rate constant of 10s—109 Lmol V1 [4], Therefore, the initiated chain oxidation of aldehyde includes the following elementary steps at high dioxygen pressures [4-7] ... 

Sometimes acylium ions lose carbon monoxide to generate an ordinary carbonium ion. It will be recalled that free acyl radicals exhibit similar behavior at high temperatures. Whether or not the loss of carbon monoxide takes place seems to depend on the stability of the resulting carbonium ion and on the speed with which the acylium ion is removed by competing reactions. Thus no decarbonylation is observed in Friedel-Crafts reactions of benzoyl chloride, the phenyl cation being rather unstable. But attempts to make pivaloyl benzene by the Friedel-Crafts reaction produce tert-butyl benzene instead. With compound XLIV cyclization competes with decarbonylation, but this competition is not successful in the case of compound XLV in which the ring is deactivated.263... 

The method used by Bawn and Mellish relies on the presence of a radical trap in the reaction mixture, that is, a compound that reacts very fast with the acyl radicals produced, thus preventing their recombination. This substance was the vivid colored 2,2-diphenyl-1-picrylhydrazyl radical (figure 15.1). When these nitrogen-centered radicals, herein abbreviated by P, react with an acyl radical (reaction 15.6), the solution color change can be monitored with a spectrophotometer. 

In addition to studying the behavior of benzoyl chloride. Cheek and Horine [72] have examined the reduction of benzoyl fluoride electrolysis of the latter compound affords benzyl benzoate, diphenyl-acetylene, stilbenol benzoate, and some polymers. Another feature of the reduction of benzoyl chloride is the possibility that both acyl radicals and acyl anions are involved as intermediates [71]. 

Phenylacetyl chloride and hydrocin-namoyl chloride are reduced at mercury to form both acyl radicals and acyl anions as intermediates [76]. From electrolyses of phenylacetyl chloride, the products include 1,4-diphenyl-2-butene-2,3-diol diphenylac-etate, phenylacetaldehyde, toluene, 1,3-diphenylacetone, and l,4-diphenyl-2,3-butanediol, and analogous species arise from the reduction of hydrocinnamoyl chloride. Reduction of phthaloyl dichloride is a more complicated system [77] the electrolysis products are phthalide, biph-thalyl, and 3-chlorophthalide, but the latter compound undergoes further reduction to give phthalide, biphthalyl, and dihydrobi-phthalide. 

Elimination to yield alkenes can be induced thermally or by treatment with acids or bases (for one possible mechanism, see Figure 3.39) [138,206]. Less common thermal demetallations include the thermolysis of arylmethyloxy(phenyl)carbene complexes, which can lead to the formation of aryl-substituted acetophenones [276]. Further, (difluoroboroxy)carbene complexes of molybdenum, which can be prepared by treating molybdenum hexacarbonyl with an organolithium compound and then with boron trifluoride etherate at -60 °C, decompose at room temperature to yield acyl radicals [277]. 

The described imidoylation of a-acyl radicals deserves great interest since a-acyl compounds are not only versatile building blocks but also exhibit several biological activities. ... 

Tris[(2-perfluorohexyl)ethyl]tin hydride has three perfluorinated segments with ethylene spacers and it partitions primarily (> 98%) into the fluorous phase in a liquid-liquid extraction. This feature not only facilitates the purification of the product from the tin residue but also recovers toxic tin residue for further reuse. Stoichiometric reductive radical reactions with the fluorous tin hydride 3 have been previously reported and a catalytic procedure is also well established. The reduction of adamantyl bromide in BTF (benzotrifluoride) " using 1.2 equiv of the fluorous tin hydride and a catalytic amount of azobisisobutyronitrile (AIBN) was complete in 3 hr (Scheme 1). After the simple liquid-liquid extraction, adamantane was obtained in 90% yield in the organic layer and the fluorous tin bromide was separated from the fluorous phase. The recovered fluorous tin bromide was reduced and reused to give the same results. Phenylselenides, tertiary nitro compounds, and xanthates were also successfully reduced by the fluorous fin hydride. Standard radical additions and cyclizations can also be conducted as shown by the examples in Scheme 1. Hydrostannation reactions are also possible, and these are useful in the techniques of fluorous phase switching. Carbonylations are also possible. Rate constants for the reaction of the fluorous tin hydride with primary radicals and acyl radicals have been measured it is marginally more reactive than tributlytin hydrides. ... 

The simplest vapor phase reaction of aliphatic carbonyl compounds in their triplet states is cleavage into acyl and alkyl radicals. The acyl radicals, especially at high temperatures, eventually decar-bonylate. 

ACYLATION. A reaction or process whereby an acyl radical, such as acetyl, benzoyl, etc., is introduced into an organic compound. Reagents often used for acylation are the acid anhydride, add chloride, or the acid of the particular acyl radical to be introduced into the compound. 

Free-radical-mediated four-component coupling reactions are rare. However, when an allyltin-mediated radical carbonylation is conducted in the presence of electron-deficient alkenes, four-component coupling reactions take place efficiently to give good yields of p-functionalized <5,fi-unsaturated ketones [40]. The wide scope of this four-component coupling reaction is noteworthy Primary, secondary, and tertiary alkyl bromides and iodides can be used as well as aromatic and vinylic halides. A variety of electron-deficient alkenes, such as methyl vinyl ketone, ethyl acrylate, acrolein, acrylonitrile, and vinyl sulfone, can be used as the acyl radical trap (Scheme 6.23). Fluorous allyltin compounds can also be used in four-component coupling reactions [41]. 

One-electron oxidation systems can also generate radical species in non-chain processes. The manganese(III)-induced oxidation of C-H bonds of enolizable carbonyl compounds [74], which leads to the generation of electrophilic radicals, has found some applications in multicomponent reactions involving carbon monoxide. In the first transformation given in Scheme 6.49, a one-electron oxidation of ethyl acetoacetate by manganese triacetate, yields a radical, which then consecutively adds to 1-decene and CO to form an acyl radical [75]. The subsequent one-electron oxidation of an acyl radical to an acyl cation leads to a carboxylic acid. The formation of a y-lactone is due to the further oxidation of a carboxylic acid having an active C-H bond. As shown in the second equation, alkynes can also be used as substrates for similar three-component reactions, in which further oxidation is not observed [76]. 

Figure 6.3 Catalase redox transformation diagram. Compounds II, III and IV represent complexes of the enzyme with H202 and iron valence states, Fe5+, Fe4+ and Fe6+, respectively HXOH is a two-electron donor (reducer) X=0, NH, C=0, H(CH2) CH, where n = 1,2, 3 AH is a single-electron donor (reducer) ROOH is hydroperoxide (R is alkyl or acyl radical) and ROH is alcohol.

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. 

A tandem carbonylation-cyclization radical process in heteroaromatic systems bearing electron-attracting substituents such as l-(2-iodoethyl)indoles and pyrroles 970 result in the formation of 2,3-dihydto-l//-pyrrolo[l,2- ]indol-1-ones and 2,3-dihydro-l//-pyrrolizin-l-ones 974 (Scheme 188). The AIBN-induced radical reaction of compounds 970 with Bu3SnH under pressure of CO suggests that the acyl radical 972, derived from radical 971 and CO, would undergo intramolecular addition to C-2 of heteroaromatic system, and the benzylic radical 973 so obtained, upon in situ oxidation would produce final product 974 <1999TL7153>. 

The magnitudes of both SCRP and RPM polarization patterns depend on the rate of encounters taking between the two radical centers. Polymeric radical a and oxo-acyl radical b have drastically different diffusional properties in solution. Radical b is small and will undergo much more rapid diffusion than a. An immediate consequence of this is that RPM and SCRP polarization mechanisms may be quenched by relatively slow reencounter rates and will therefore be obscured in this case by the very strong TM. In all TREPR spectra detected here, emissive TM is always observed, which is unusual for aliphatic carbonyl compounds, although not unprecedented for esters. 

The treittment of polyfluoroacyl chlorides with stoichiometric amounts of tctrucarbonyl-nickcl(O) at ca. 150 C resulted in decarbonylation of acyl radicals. When such reactions were carried out in an aromatic hydrocarbon medium, polyfluoroalkyl-subslitutcd aromatic compounds. e.g, 4. were obtained. The aromatic compounds used were benzene, toluene or bro-mobenzene. ... 

The main difficulty with the mirror techniques as a quantitative tool lies in the extreme sensitivity of the mirrors to contamination by oxygen, nitrogen, parent compounds, or other radicals. Thus in the photolysis of ketones and fatty acids the original reactants as well as acyl radicals are capable of desensitizing the mirror unless it is heated above 100°C. Another difficulty is that the mirror may not only react with the free radicals but also catalyze secondary reactions and recombination of radicals. 

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