C electrophilic addition

Scheme 4. The variously proposed alternative reaction mechanisms for heme dioxygenases, (a) The base-catalyzed abstraction mechanism (21,49). (b) An alternative to the base-catalyzed mechanism, using proton abstraction by the bound O2 (23,27). (c) Electrophilic addition (31,50,51). (d) Radical addition (50-53). The majority opinion from crystallography (27), mass spectrometry (30), mutagenesis (54), and computational work (50) concludes that (a) and (b) are unlikely. It is not yet known whether addition at C or is most likely both have been suggested (31,50-53,55).

Regioselective C-electrophilic addition of isocyanates and isothiocyanates to 2-sub-stituted 1/f-perimidines 601 were carried out by refluxing in anhydrous acetonitrile for a long time (15-163 h) to afford 602 in 66 94% yields. When the addition was carried out under solvent-free conditions using either MWI or an oil bath, the yields were increased to 99% and the times were reduced to 10 25 min (Scheme 118) (96BSF587). 

Both resonance forms of the allylic carbocation from 1 3 cyclopentadiene are equivalent and so attack at either of the carbons that share the positive charge gives the same product 3 chlorocyclopentene This is not the case with 1 3 butadiene and so hydrogen halides add to 1 3 butadiene to give a mixture of two regioisomeric allylic halides For the case of electrophilic addition of hydrogen bromide at -80°C... 

Electrophilic addition to quinones, eg, the reaction of 2-chloro-l,4-ben2oquinones with dia2onium salts, represents a marked contrast with acetoxylation in product distribution (58). Phenyldia2onium chloride (Ar = C H ) yields 8% 2,3-substitution [80632-59-3] 75% 2,5-substitution [39171-11-4] and 17% 2,6-substitution [80632-60-6]. Fory)-chlorophenyldia2onium chloride, the pattern is 28% 2,3-substitution [80632-61-7], 35%... 

Fluorination with XeF2 or C H IF2 gives both the 1,2- and 1,4-difluoro products. This reaction proceeds via the initial electrophilic addition of F to the diene (53). 

In addition to electrophilic attack on the pyrrole ring in indole, there is the possibility for additions to the fused benzene ring. First examine the highest-occupied molecular orbital (HOMO) of indole. Which atoms contribute the most What should be the favored position for electrophilic attack Next, compare the energies of the various protonated forms of indole (C protonated only). These serve as models for adducts formed upon electrophilic addition. Which carbon on the pyrrole ring (C2 or C3) is favored for protonation Is this the same as the preference in pyrrole itself (see Chapter 15, Problem 2)1 If not, try to explain why not. Which of the carbons on the benzene ring is most susceptible to protonation Rationalize your result based on what you know about the reactivity of substituted benzenes toward electrophiles. Are any of the benzene carbons as reactive as the most reactive pyrrole carbon Explain. 

What evidence is there to support the carbocation mechanism proposed for the electrophilic addition reaction of alkenes One of the best pieces of evidence was discovered during the 1930s by F. C. Whitmore of the Pennsylvania State University, who found that structural rearrangements often occur during the reaction of HX with an alkene. For example, reaction of HC1 with 3-methyl-1-butene yields a substantial amount of 2-chloro-2-methylbutane in addition to the "expected" product, 2-chloro-3-methylbutane. 

The following carbocation is an intermediate in the electrophilic addition reaction of HCl with two different alkenes. Identify both, and tell which C-H bonds in the carbocation are aligned for hyperconjugation with the vacant p orbital on the positively charged carbon. 

Electrophilic addition to a conjugated diene at or below Toom temperature normally leads to a mixture of products in which the 1,2 adduct predominates over the 1,4 adduct. When the same reaction is carried out at higher temperatures, though, the product ratio often changes and the 1,4 adduct predominates. For example, addition of HBr to 1,3-butadiene at 0°C yields a 71 29 mixture of 1,2 and 1,4 adducts, but the same reaction carried out at 40 °C yields a 15 85 mixture. Furthermore, when the product mixture formed at 0 °C is heated to 40 °C in the presence of HBr, the ratio of adducts slowly changes from 71 29 to 15 85. Why ... 

The mechanism of the alkoxymercuration reaction is similar to that described in Section 7.4 for hvdroxymercuration. The reaction is initiated by electrophilic addition of Iig2+ to the alkene, followed by reaction of the intermediate cation with alcohol and reduction of the C-Hg bond by NaBH4. A variety of alcohols and alkenes can be used in the alkoxymercuration reaction. Primary, secondary, and even tertiary alcohols react well, but ditertiary ethers can t be prepared because of steric hindrance to reaction. 

A remarkably rigid molecule in which the ring rotation is locked up to 100 °C was found in the form of Co(Bu2Cp)(PMe3)2 (11) [36]. This complex was synthesized as a brown oil by electrophilic addition of ferf-butyl bromide to Co(BuCp)(PMe3)2 followed by deprotonation of similarly rigid [Co(Bu2Cp)-... 

The primary attack of an electrophile takes place during both the electrophilic addition to olefines and the cationic polymerization resulting in the formation of a car-benium ion R—C+H—CH3 as a reactive intermediate from the olefine or monomer R—CH=CH2 72) (Eq. 16). In the simplest of cases, the electrophile is a proton. 

The reactivity of a remarkable electronically unsaturated tantalum methyli-dene complex, [p-MeCgH4C(NSiMe3)2]2Ta( = CH2)CH3, has been investigated. Electrophilic addition and olefination reactions of the Ta = CH2 functionality were reported. The alkylidene complex participates in group-transfer reactions not observed in sterically similar but electronically saturated analogs. Reactions with substrates containing unsaturated C-X (X = C, N, O) bonds yield [Ta] = X compounds and vinylated organic products. Scheme 117 shows the reaction with pyridine N-oxide, which leads to formation of a tantalum 0x0 complex. ... 

If the carbanion has even a short lifetime, 6 and 7 will assume the most favorable conformation before the attack of W. This is of course the same for both, and when W attacks, the same product will result from each. This will be one of two possible diastereomers, so the reaction will be stereoselective but since the cis and trans isomers do not give rise to different isomers, it will not be stereospecific. Unfortunately, this prediction has not been tested on open-chain alkenes. Except for Michael-type substrates, the stereochemistry of nucleophilic addition to double bonds has been studied only in cyclic systems, where only the cis isomer exists. In these cases, the reaction has been shown to be stereoselective with syn addition reported in some cases and anti addition in others." When the reaction is performed on a Michael-type substrate, C=C—Z, the hydrogen does not arrive at the carbon directly but only through a tautomeric equilibrium. The product naturally assumes the most thermodynamically stable configuration, without relation to the direction of original attack of Y. In one such case (the addition of EtOD and of Me3CSD to tra -MeCH=CHCOOEt) predominant anti addition was found there is evidence that the stereoselectivity here results from the final protonation of the enolate, and not from the initial attack. For obvious reasons, additions to triple bonds cannot be stereospecific. As with electrophilic additions, nucleophilic additions to triple bonds are usually stereoselective and anti, though syn addition and nonstereoselective addition have also been reported. 

Perhaps the most characteristic property of the carbon-carbon double bond is its ability readily to undergo addition reactions with a wide range of reagent types. It will be useful to consider addition reactions in terms of several categories (a) electrophilic additions (b) nucleophilic additions (c) radical additions (d) carbene additions (e) Diels-Alder cycloadditions and (f) 1,3-dipolar additions. 

The formation of any vinyl products in electrophilic additions to RCH=C=CH2 and RCH=C=CHR is surprising, since central protonation should yield a secondary carbonium ion compared to terminal protonation and formation of a vinyl cation. Perhaps a secondary carbonium ion destabilized by... 

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