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Radicals addition to multiple bonds

Firstly, it has long been realized that geometry optimizations and frequency calculations are generally less sensitive to the level of theory than are energy calculations. For example, as will be discussed in a following section, detailed assessment studies (36,37) have shown that even HF/6-31G(d) can provide reasonable approximations to the considerably more expensive CCSD(T)/6-311 -i- G(d,p) level of theory, for the geometries and frequencies of the species in radical addition to multiple bonds (such as C=C, C=C, and C=S). By contrast, very high levels of... [Pg.1728]

In Part 2 of this book, we shall be directly concerned with organic reactions and their mechanisms. The reactions have been classified into 10 chapters, based primarily on reaction type substitutions, additions to multiple bonds, eliminations, rearrangements, and oxidation-reduction reactions. Five chapters are devoted to substitutions these are classified on the basis of mechanism as well as substrate. Chapters 10 and 13 include nucleophilic substitutions at aliphatic and aromatic substrates, respectively, Chapters 12 and 11 deal with electrophilic substitutions at aliphatic and aromatic substrates, respectively. All free-radical substitutions are discussed in Chapter 14. Additions to multiple bonds are classified not according to mechanism, but according to the type of multiple bond. Additions to carbon-carbon multiple bonds are dealt with in Chapter 15 additions to other multiple bonds in Chapter 16. One chapter is devoted to each of the three remaining reaction types Chapter 17, eliminations Chapter 18, rearrangements Chapter 19, oxidation-reduction reactions. This last chapter covers only those oxidation-reduction reactions that could not be conveniently treated in any of the other categories (except for oxidative eliminations). [Pg.381]

The thiocarbonyl group is excellent for radical addition, which takes place on the sulfur atom and leads to a carbon-centred radical stabilised by the a-sulfur atom. The Barton reaction has enjoyed a great many applications. It mainly involves xanthates and provides many useful processes, such as deoxygenation, decarboxylation, addition to multiple bonds, etc. A number of reviews by Crich et al. have appeared [188, 189], and the most recent is due to Zard [190]. [Pg.152]

During a microsecond time frame, which is the typical paramagnetic relaxation time of free radicals, polarized free radicals can participate in addition to multiple bonds, to dioxygen, in hydrogen (electron) transfer, in addition to polyradicals, etc. Products of these reactions are polarized in most cases, and they demonstrate TR ESR signals. [Pg.276]

Despite these complications, the enormous and unique synthetic potential of radical reactions is also obvious. Radicals are highly reactive species and their addition to multiple bonds occurs easily, even with crowded substrates, under mild and essentially neutral conditions. Radical reactions are not generally sensitive to the influence of polar effects and tolerate the presence of functional groups otherwise incompatible with electrophilic and/or nucleophilic reagents. [Pg.199]

On descending groups IVB, VB, and VIB, the increasing weakness of the M—H bond favors formation of the M radical and therefore facilitates radical chain additions to multiple bonds. However, the increasing rate of homocoupling of M- radicals relative to their rate of attack on alkenes leads to increasing loss of reagent via ... [Pg.562]

Additions to multiple bonds catalyzed by radical initiators produce novel synthetic methods. Carboxylic acids add to acetylenic compounds in the presence of organic peroxides. Acetic acid and acetylene yield adipic acid 1-hexyne and acetic acid give octen-3-oic acid. Radical amination of olefins with hydroxylamine sulfonic acid and hydroxylamine in the presence of FeCla gives the corresponding l-amino-2-chloro compounds. ... [Pg.323]

The second important type of propagation reaction is addition to multiple bonds addition to C=C is particularly important. In reaction (6.34), R can be an atom or a group centred on carbon or any element which forms a bond stronger than the n bond which is broken in the reaction (about 250 kJ mol-1). If the alkene is unsymmetrical, addition can in principle take place at either end of the double bond. Addition normally takes place at the end of the double bond which will generate the more stable free radical. Thus for addition of a halogen atom to propene, attack at the CH2 position will give the secondary radical 47 (reaction 6.35) rather than attack at the central carbon atom which would give the less stable primary radical 48 (reaction 6.36). [Pg.139]

The most important reactions of radicals are atom abstraction and addition to multiple bonds. Atom abstraction is almost always hydrogen or halogen. [Pg.147]

Based on the early studies of radical generation from organotin hydrides and their addition to multiple bonds [1-3], particnlarly in cyclization [4-7], several groups applied this chemistry to the synthesis of indoles and indolines. For example, in 1975 Beckwith and colleagues found that < -(A -allyl-Af-methylamino)iodobenzene was converted to 1,3-dimethylindoline (78% yield) upon treatment with tri-n-butylstannane (prepared by the reduction of tri-n-butyltin chloride with LiAlH ) in the presence of AIBN (azobisisobutyronitrile) and benzene at 130°C in a sealed tube [4],... [Pg.405]

The effect of multiplicity of carbenes on their reactivity is most vividly marked in the following features rationalized by Skell et al. from experimental data [37-39]. First, the reaction of carbenes occurs in the singlet electron state at a much faster rate than in the triplet, with the absolute rates of typical reactions of addition to multiple bonds and of insertion into the C—H bonds exceeding, under normal conditions, the rate of intercombination conversion. Secondly, the singlet carbenes are characterized by one-step stereospecific addition to double bonds, as, for instance, in the cyclopropanation reaction, while the triplet carbenes react in a nonstereospecific way to form first an intermediate biradical through addition to one of the atoms of the double bond. The formation of a trimethylene radical, in the course of reaction of triplet methylene ( B ) with ethylene, has been confirmed by semiempirical [40, 41] and ab initio [42, 43] quantum chemical calculations. [Pg.200]

Absolute rate constants for the addition of a sulfonyl radical to multiple bonds are absent from the literature. However, there are some relative kinetic data. Correa and... [Pg.1102]

Parameters of Various Classes of the Addition of Atoms and Radicals to Multiple Bonds Used in the Parabolic Model [40-45]... [Pg.270]

Nucleophilic substitution reactions of sulfinate ions 106 Addition of sulfinate ions to multiple bonds 108 Radical reactions of sulfinic acids 110... [Pg.65]

Hydrosilylation, the addition of a silicon-hydrogen bond to multiple bonds, is a valuable laboratory and industrial process in the synthesis of organosilicon compounds. The addition to carbon-carbon multiple bonds can be accomplished as a radical process initiated by ultraviolet (UV) light, y irradiation, or peroxides. Since the discovery in the 1950s that chloroplatinic acid is a good catalyst to promote the addition, metal-catalyzed transformations have become the commonly used hydrosi-... [Pg.322]

This chapter begins with an introduction to the basic principles that are required to apply radical reactions in synthesis, with references to more detailed treatments. After a discussion of the effect of substituents on the rates of radical addition reactions, a new method to notate radical reactions in retrosynthetic analysis will be introduced. A summary of synthetically useful radical addition reactions will then follow. Emphasis will be placed on how the selection of an available method, either chain or non-chain, may affect the outcome of an addition reaction. The addition reactions of carbon radicals to multiple bonds and aromatic rings will be the major focus of the presentation, with a shorter section on the addition reactions of heteroatom-centered radicals. Intramolecular addition reactions, that is radical cyclizations, will be covered in the following chapter with a similar organizational pattern. This second chapter will also cover the use of sequential radical reactions. Reactions of diradicals (and related reactive intermediates) will not be discussed in either chapter. Photochemical [2 + 2] cycloadditions are covered in Volume 5, Chapter 3.1 and diyl cycloadditions are covered in Volume 5, Chapter 3.1. Related functional group transformations of radicals (that do not involve ir-bond additions) are treated in Volume 8, Chapter 4.2. [Pg.716]

Intermolecular free-radical additions of stannyl radicals to multiple bonds have emerged as important methods for the preparation of tetraorganostannanes which can be reacted further to afford new C—C bonds through transition metal mediated coupling processes (e.g. Stille coupling). There are numerous examples of this chemistry715-737, and this treatise will focus on a few selected examples. [Pg.1449]

Meerwein type arylations involving radical additions to carbon-heteroatom multiple bonds such as in isothiocyanates have been further extended to tandem reactions leading to heterocycles [117, 118]. [Pg.46]

The addition of (TMS SiH across carbon-carbon multiple bonds under free-radical conditions is well documented82. Although no recent reports of such hydrosilylation processes are reported, the addition of (TMS Si radical to multiple bonds, followed by other radical reactions, were investigated (vide infra). The hydrosilylation of ketones and aldehydes is also well known83. In this respect Brook and coworkers have recently shown that the (TMS)3Si group can be used for the protection of primary and secondary alcohols84. [Pg.368]


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See also in sourсe #XX -- [ Pg.765 , Pg.766 , Pg.767 , Pg.768 , Pg.769 ]

See also in sourсe #XX -- [ Pg.4 , Pg.765 , Pg.766 , Pg.767 , Pg.768 , Pg.769 ]

See also in sourсe #XX -- [ Pg.4 , Pg.765 , Pg.766 , Pg.767 , Pg.768 , Pg.769 ]




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