Radicals reactivity pattern

More so than any other area of reactive intermediate chemistry, thermodynamics is a valuable predictor of radical reactivity. There will always be exceptions, and we can never totally ignore kinetics, but as a first step, we will in most instances turn to the thermochemistry of a given sifuation to predict or rationalize radical reactivity patterns. In addition, there is a vast collection of relevant thermodynamic data for radicals—the collection of BDEs discussed in Section 2.1.3. 

In order to understand the physical properties and reactivity patterns of S-N compounds it is particularly instructive to compare their electronic structures with those of the analogous organic systems.On a qualitative level, the simplest comparison is that between the hypothetical HSNH radical and the ethylene molecule each of these units can be considered as the building blocks from which conjugated -S=N- or -CH=CH-systems can be constructed. To a first approximation the (j-framework of... 

Reactivity patterns of radical cations in transformations of heterocycles 97AG(E)2550. 

The evaluation of this family of rate constants for various molecules RH was of interest, since it would define the reactivity pattern in Eq. (3-90). To do so, an appropriate concentration of carbon tetrachloride was added prior to each thermolysis. It, too, reacts with phenyl radicals ... 

From the point of view of both synthetic and mechanistic interest, much attention has been focused on the addition reaction between carbenes and alkenes to give cyclopropanes. Characterization of the reactivity of substituted carbenes in addition reactions has emphasized stereochemistry and selectivity. The reactivities of singlet and triplet states are expected to be different. The triplet state is a diradical, and would be expected to exhibit a selectivity similar to free radicals and other species with unpaired electrons. The singlet state, with its unfilled p orbital, should be electrophilic and exhibit reactivity patterns similar to other electrophiles. Moreover, a triplet addition... 

The radical versus electrophilic character of triplet and singlet carbenes also shows up in relative reactivity patterns given in Table 10.1. The relative reactivity of singlet dibromocarbene toward alkenes is more similar to electrophiles (bromination, epoxidation) than to radicals ( CCl,). 

The early studies of the chemical effects of ultrasound have been thoroughly reviewed (5-7). Only the most important and most recent research is mentioned here as needed to provide a perspective on sonochemical reactivity patterns. The sonolysis of water is the earliest and most exhaustively studied (3,93,96,98-105). The first observations on the experimental parameters which influence sonochemistry come from these reports. The primary products are H202 and H2, and various data supported their formation from the intermediacy of hydroxyl radicals and hydrogen radicals ... 

Closs and Trifunac, 1970 Baldwin and Andrist, 1971 Lepley and Closs, 1972 Bethell and McDonald, 1977). The formation of free radicals from aromatic carbenes is often easily detected by the fast laser spectroscopic techniques discussed earlier. The radicals generally have characteristic absorption spectra and reactivity patterns that make their identification certain. The direct insertion reaction of singlet carbenes is not expected to generate free radicals. 

The general idea of this concept was first outlined by Nugent and Rajan-Babu [17-20] as shown in Scheme 3, and constitutes an analogue of the well-established opening of a cyclopropylcarbinyl radical [21,22]. Titanocenes have emerged as the most powerful reagents in these transformations. However, it is clearly attractive to find other metal complexes in order to develop novel reactivity patterns. 

Aryl- and alkylsulfonyl radicals have been generated from the corresponding iodides and added to, e.g., propadiene (la), enantiomerically enriched (P)-(+)-propa-2,3-diene [(P)-(lc)] and (P)-(-)-cyclonona-l,2-diene [(P)-(lk)] [47]. Diaddition of sulfo-nyl radicals may compete considerably with the monoaddition [48,49]. Also, products of diiodination have been purified from likewise obtained reaction mixtures, which points to a more complex reactivity pattern of these substrates towards cumulated Jt-bonds. An analysis of regioselectivities of arylsulfonyl radical addition to allenes is in agreement with the familiar trend that a-addition occurs in propadiene (la), whereas alkyl-substitution at the cumulated Jt-bond is associated with a marked increase in formation of /3-addition products (Scheme 11.7). 

Vanoppen et al. [88] have reported the gas-phase oxidation of zeolite-ad-sorbed cyclohexane to form cyclohexanone. The reaction rate was observed to increase in the order NaY < BaY < SrY < CaY. This was attributed to a Frei-type thermal oxidation process. The possibility that a free-radical chain process initiated by the intrazeolite formation of a peroxy radical, however, could not be completely excluded. On the other hand, liquid-phase auto-oxidation of cyclohexane, although still exhibiting the same rate effect (i.e., NaY < BaY < SrY < CaY), has been attributed to a homolytic peroxide decomposition mechanism [89]. Evidence for the homolytic peroxide decomposition mechanism was provided in part by the observation that the addition of cyclohexyl hydroperoxide dramatically enhanced the intrazeolite oxidation. In addition, decomposition of cyclohexyl hydroperoxide followed the same reactivity pattern (i.e., NaY < BaY... 

The radical versus electrophilic character of triplet and singlet carbenes also shows up in relative reactivity patterns shown in Table 10.1. The relative reactivity of singlet dibromocarbene toward alkenes is more similar to that of electrophiles (bromination, epoxidation) than to that of radicals ( CC13). Carbene reactivity is strongly affected by substituents.61 Various singlet carbenes have been characterized as nucleophilic, ambi-philic, and electrophilic as shown in Table 10.2. This classification is based on relative reactivity toward a series of different alkenes containing both nucleophilic alkenes, such as tetramethylethylene, and electrophilic ones, such as acrylonitrile. The principal structural feature that determines the reactivity of the carbene is the ability of the substituents to act as electron donors. For example, dimethoxycarbene is devoid of electrophilicity toward... 

We have demonstrated that intermolecularly, amidyl radicals preferentially abstract an allylic hydrogen rather than add to a TT bond of olefins such as cyclohexene and 1,3-pentadiene (33). This reactivity pattern is completely reversed in intramolecular reactions as shown in the following examples of alkenyl mitro-samide photolysis. In every case, the amidyl radicals generated from photolysis preferentially attack the ir bonds intramolecu-... 

The advances made in using free radicals as synthetic intermediates in die last 10-20 years have been extraordinary due to new methods to effectively generate free radicals and new insights into their reactivity patterns which allow them to be controlled. As a consequence, the construction of ring systems has been tremendously facilitated. 

Schmittel M,Ghorai MK(2001) Reactivity patterns of radical ions-a unifying picture of radical-anion and radical-cation transformations. In Balzani V (ed) Electron transfer in chemistry, vol 2. Organic molecules. Wiley-VCH, Weinheim, pp 5-54... 

Schmittel M, Ghorai MK (2001) Reactivity patterns of radical ions - a unifying picture of radical-anion and radical-cation transformations. In Balzani V (ed) Electron transfer in chemistry, vol 2. Organic molecules. Wiley-VCH, Weinheim, pp 5-54 Schoneich C, Bonifacic M, Dillinger U, Asmus K-D (1990) Hydrogen abstraction by thiyl radicals from activated C-H-bond of alcohols, ethers and polyunsaturated fatty acids. In Chatgilialoglu C, Asmus K-D (eds) Sulfur-centered reactive intermediates in chemistry and biology. Plenum, New York, pp 367-376... 

The success of the modified patterns treatment shows that radical reactivities in the gas phase are governed to a major extent by polar forces as given quantitative expression in the Hammett equation. These correlations support the conclusions reached in earlier sections that both the polarity of the alkene and the polar character of the radical are important. They also help to establish a common pattern of behaviour for radicals in gas-phase addition reactions and in liquid-phase polymerization processes. 

Among more recent innovations, the alkylative metallacyclobutane and metallacyclobutene synthesis, involving central carbon addition and addition/elimination reactivity patterns, holds considerable promise for near-term synthetic developments (Section 2.12.12). This is equally true in both the nucleophilic and free radical versions of this process, for both catalytic and stoichiometric transformations and multistep reaction cascades. 

Pyridines undergo radical substitution reactions preferentially at the 2-position. Yields and regioselectivity are generally higher if the reaction is carried out in an acid medium. The presence of a strongly electron-donating substituent (OH, OR, NR2) on the pyridine ring can alter the reactivity pattern of electrophilic and radical substitution. 

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