Carboxylic acid derivatives reactions with organometallic

Acidity of Amides, Imides, and Sulfonamides Characteristic Reactions Reaction with Water Hydrolysis Reaction with Alcohols Reactions with Ammonia and Amines Reaction of Acid Chiorides with Salts of Carboxylic Acids Interconversion of Functional Derivatives Reactions with Organometallic Compounds 18.10 Reduction... 

The reaction of carbon nucleophiles derived from organometallics with carboxylic acid derivatives follows closely the reactions we have already encountered in Sections 6.3.2 and 7.6.2. Organometallics... 

Acylation is one of the most fundamental and useful reactions in organic synthesis and is normally achieved by the reaction either with carboxylic acid derivatives and organometallic compounds or with masked acyl anions and aUcyl halides. 

The reactions of several carboxylic acid derivatives with organomagnesium and organolithium compounds were described in Section 14-12. The key step in these reactions is addition of the organometallic compound, as R60MS , to the carbonyl group. For a Grignard reagent,... 

First, the general mechanisms for these reactions are presented. Then the reactivity of these carboxylic acid derivatives is discussed. As expected, the factors that control the reactivity are very similar to those that affect the addition reactions of Chapter 18. Next, reactions with nucleophiles that interconvert all of the members of the carboxylic acid family are presented. Finally, the reactions of hydride and organometallic nucleophiles with these electrophiles are discussed. 

By using the reactions described in Sections 19.2 through 19.6, it is possible to convert one carboxylic acid derivative to any other carboxylic acid derivative. Now let s examine the reactions of these compounds with hydride and organometallic nucleophiles. In these cases the products are no longer carboxylic acid derivatives. 

Predict the products and propose mechanisms for the reactions of carboxylic acid derivatives with reducing agents, alcohols, amines, and organometallic reagents. Q Propose multistep syntheses using acid derivatives as starting materials and intermediates. 

Reaction of organometallic reagents with carboxylic acid derivatives... 

Reaction of Organometallic Reagents with Carboxylic Acid Derivatives... 

Organometallic reagents react with carboxylic acid derivatives (RCOZ) to form two different products, depending on the identity of both the leaving group Z and the reagent R-M. The most useful reactions are carried out with esters and acid chlorides, forming either ketones or 3° alcohols. 

Reaction of organometallics bearing an a-seleno carbanion with carboxylic acid derivatives and related... 

In 1957, Schlogl reported the synthesis and characterization of several ferrocene amino acids, including ferrocenylala-nine (Fer, 14 Scheme 18). Other organometallic amino acids include alanine, phenylalanine (Phe), glycine derivatives, as well as further ferrocene-based amino acids, which are discussed below. The Schlogl paper also describes the reaction of ferrocene carboxylic acid and ferrocene carbaldehyde with amino acids. The chemistry was later picked up in numerous publications, and ferrocene carboxylic acid amides or ferrocene imines with basically all amino acids and many dipeptides were reported. Such conju tes may serve as ligands for other transition metal ions. " Kraatz has prepared ferrocene carboxylic acid conju tes with short peptides that serve as enzyme inhibitors. ... 

This chapter will discuss methods for the preparation of esters, acid chlorides, anhydrides, and amides from carboxylic acids, based on acyl substitution reactions. Acyl substitution reactions of carboxylic acid derivatives will include hydrolysis, interconversion of one acid derivative into another, and reactions with strong nucleophiles such as organometallic reagents. In addition, the chemistry of dicarboxylic acid derivatives will be discussed, as well as cyclic esters, amides, and anhydrides. Sulfonic acid derivatives will be introduced as well as sulfate esters and phosphate esters. Finally, nitriles will be shown to be acid derivatives by virtue of their reactivity. 

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