Addition reactions carbanion intermediates

There are two potential advantages of using a mixture of methanol and ethanol. First, the much lower cost of methanol allows its use in large excess so that very high conversions of ethanol might be obtained. Second, dehydrogenation of methanol produces formaldehyde, which is an especially reactive additive to carbanion intermediates in the condensation reactions. 

Similar observations of base catalysis have been used to invoke the ElcB mechanism for elimination from 4,4-dicyano-3-p-nitrophenyl-1 -phenylbutan-1 -one in neutral and acidic methanol (34) , and l,l,l,3-tetranitro-2-phenylpro-pane in methanol in the presence of hydrochloric acid and pyridine-pyridine hydrochloride buffers (36) . In the former reaction, an example of a reverse Michael addition, the carbanion intermediate with the electron pair alpha to the carbonyl rather than in the gamma position is favoured, as the methyl isomer (35) eliminates more rapidly than the parent compound. 

In contrast, additions of fluorine and carbon to fluormated olefins are widely investigated The best known processes involve reactions of olefins with fluoride ion to generate carbanionic intermediates [203] that are trapped in situ by carbon-based electrophiles. 

Because of thetr electron deficient nature, fluoroolefms are often nucleophihcally attacked by alcohols and alkoxides Ethers are commonly produced by these addition and addition-elimination reactions The wide availability of alcohols and fliioroolefins has established the generality of the nucleophilic addition reactions The mechanism of the addition reaction is generally believed to proceed by attack at a vinylic carbon to produce an intermediate fluorocarbanion as the rate-determining slow step The intermediate carbanion may react with a proton source to yield the saturated addition product Alternatively, the intermediate carbanion may, by elimination of P-halogen, lead to an unsaturated ether, often an enol or vinylic ether These addition and addition-elimination reactions have been previously reviewed [1, 2] The intermediate carbanions resulting from nucleophilic attack on fluoroolefins have also been trapped in situ with carbon dioxide, carbonates, and esters of fluorinated acids [3, 4, 5] (equations 1 and 2)... 

The nucleophilic reaction of bromotrifluoroethene with alkoxides yields not only the expected addition and addition-elimination products but also a product from a bromophilic reaction of the carbanion intermediate [6] (equation 3) Similar are the reactions of sodium phenoxide with perfluorovinyl ethers in the presence of hexachloroethane or selected vicinal dibromoperfluoroalkanes The intermediate carbanion is trapped in high yield by these sources of Cl or Br, which suggests a... 

Two types of intermediates, i.e., radicals or carbanions or their organometallic equivalents, can be used to perform addition reactions to Michael acceptors. The free-radical route has already been investigated with nickel or cobalt complexes as catalysts [62-64]. These studies have been reinvestigated recently with the aim of improving the turn-over of the catalyst and/or using easily prepared cheap complexes. 

The stereoselectivity of anti-Markovnikov adducts (161) and (162) produced through photo-induced electron-transfer reaction of (160) with MeOH in MeCN depends on the optimum structures and stabilities of the corresponding radical and carbanion intermediates (163) and (164). In PhH, steric hindrance in an exciplex, comprising an excited singlet sensitizer and (160), forced cis addition of MeOH to (160) to give trans-isomer (161) as the major addition product. 

Considerable evidence for the existence of a carbanion intermediate in the isotopic exchange reactions of p3U idine 1-oxides is available. Treatment of 4-chloro-3-methylpyridine 1-oxide (61), for example, with w-butyllithium gives an intermediate which reacts with cyclohexanone to give 62. In addition Tupitsyn et al. have found a linear... 

The Dow Process utilizes an elimination/addition reaction to convert chlorobenzene to phenol. The proposed mechanism for this reaction is shown in Figure 8-3. The high-temperature reaction begins with chlorobenzene and aqueous sodium hydroxide. Note that this mechanism starts with the hydroxide attacking as a base, beginning dehydrohalogenation to form benzyne. The second hydroxide ion attacks as a nucleophile to form a carbanion intermediate, which behaves as a base in the last step to yield the final product. 

Carbanions play critical roles in a wide variety of reaction pathways. As stated in the Introduction, this chapter will not focus on the synthetic utility of carbanions, but will instead focus on their mechanistic significance. In this section, a sample of important reaction mechanisms that involve transient or relatively short-lived car-banion intermediates will be introduced. As you will see, the key element in these mechanisms is the ability to form a carbanion that is reasonably stable, and often the kinetics of the reactions are dominated by carbanion stability. The role of carbanion intermediates in elimination reactions will be presented in some detail as a way to illustrate some of the methods that have been developed to probe for carbanion intermediates in reaction mechanisms. Other processes including additions and rearrangement reactions will be presented in less detail, but the role of carbanion stability in these reactions will be outlined. 

An example of an a-ketol formation that does not involve decarboxylation is provided by the reaction catalyzed by transketolase, an enzyme that plays an essential role in the pentose phosphate pathway and in photosynthesis (equation 21) (B-77MI11001). The mechanism of the reaction of equation (21) is similar to that of acetolactate synthesis (equation 20). The addition of (39) to the carbonyl group of (44) is followed by aldol cleavage to give a TPP-stabilized carbanion (analogous to (41)). The condensation of this carbanionic intermediate with the second substrate, followed by the elimination of (39), accounts for the observed products (B-7IMIHOO1). 

What can follow with an alkene is an ionic chain reaction with the following two propagating steps. First, the nucleophile attacks at carbon to form a carbon anion (carbanion) intermediate (Equation 10-8). Second, electrophilic transfer of a proton from HX to the carbanion forms the adduct and regenerates the nucleophile (Equation 10-9). The overall reaction is the addition of HX to the double bond ... 

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