Organometallics sulfonate esters

The Reaction of Alkyl Halides and Sulfonate Esters With Group I (I A) and II (II A) Organometallic Reagents ... 

Reaction of Alkyl Halides and Sulfonate Esters With Other Organometallic Reagents... 

R Cu, or litliium or magnesium homocuprates RfCuM fM = Li, MgX), are fre-quently used, but a number of catalytic processes have also been developed. These processes nornnally utilize a catalytic amount of a copper salt CuY and a stoichiometric amount of an organometallic reagent R M IM = Li, MgX, ZnX, etc.). Hie leaving groups used include balides, esters, sulfonates, and epoxides, among others. 

Coupling of Organometallic Reagents With Esters of Sulfuric and Sulfonic Acids, Sulfoxides and Sulfones... 

Types of compounds are arranged according to the following system hydrocarbons and basic heterocycles hydroxy compounds and their ethers mercapto compounds, sulfides, disulfides, sulfoxides and sulfones, sulfenic, sulfinic and sulfonic acids and their derivatives amines, hydroxylamines, hydrazines, hydrazo and azo compounds carbonyl compounds and their functional derivatives carboxylic acids and their functional derivatives and organometallics. In each chapter, halogen, nitroso, nitro, diazo and azido compounds follow the parent compounds as their substitution derivatives. More detail is indicated in the table of contents. In polyfunctional derivatives reduction of a particular function is mentioned in the place of the highest functionality. Reduction of acrylic acid, for example, is described in the chapter on acids rather than functionalized ethylene, and reduction of ethyl acetoacetate is discussed in the chapter on esters rather than in the chapter on ketones. 

Esters of chlorodifluoroacetic acids, like the esters of monofluoroacetic acid, can acylate anions (e.g., organometallic derivatives, enolates, lithiated sulfones). They lead to chlorodifluoromethylketones and to S-ketosulfones and jS-ketoesters which have the —CFj motif (Figure 2.16). ... 

Unsaturated Nitriles, Nitro Compounds, and Sulfonic Acids and Esters 2-33 Cyanation of vinylic organometallic compounds... 

In most cases, treatment of allylic halides containing one ASG with a nucleophile does not result in formation of electrophilic cyclopropanes (MIRC product) instead, other reaction pathways are followed, e.g. addition, substitution, rearrangement and elimination reactions.However, with certain alkenes or nucleophiles or under the appropriate conditions a conjugate addition-nucleophilic substitution pathway is favored, resulting in cyclopropanes substituted with one ASG. Representative examples are compiled in Tables 20 and 21 where organometallic compounds or active methylene compounds are used as the nucleophilic species in combination with allyl bromides containing an ester or a sulfone as ASG. 

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