Acids, acid with organometallics

Treatment of imides of dicarboxylic acids with organometallic compounds forms cyclic enamines such as 18 and 19 (64-69). 

Reaction of Acid Chlorides with Organometallic Reagents Grignard reagents react with acid chlorides to yield tertiary alcohols in which two of the substituents are the same. 

II c., Cl 0 M L- X c Reaction of acyl halides or other acid derivatives with organometallic compounds... 

Mechanism 21-13 Hydride Reduction of an Ester 1015 Mechanism 21-14 Reduction of an Amide to an Amine 1016 21-9 Reactions of Acid Derivatives with Organometallic Reagents 1017 Mechanism 21-15 Reaction of an Ester with Two Moles of a Grignard Reagent 1018... 

Reactions of Acid Derivatives with Organometallic Reagents... 

Treatment of a thirteen-membered lactam with 1-naphthylmagnesium bromide forms both a cyclic enamine and the amino ketone412. Imides of dicarboxylic acids produce with organometallic reagents cyclic enamino compounds such as 108 (n = 1, 2)413-418. 

The nucleophilic carbanion can also be generated from 1-haloalkanesulfonic acid derivatives with organometallic reagents. a-Lithio a-chloro-4-mesylmorpholide reacts with various Michael acceptors to give morpholinosulfonyl-substituted cyclopropanes 5. 

Reaction of Acid Chlorides with Organometallic Reagents Gr ... 

Reactions of hydroximic acid esters with organometallic compds. 

The most general synthetic route to ketones uses the reaction of carboxylic acids (or their derivatives) or nitriles with organometallic compounds (M.J. Jorgenson, 1970). Lithium car-boxylates react with organolithium compounds to give stable gem-diolates, which are decom-... 

Nitriles are similar in some respects to carboxylic acids and are prepared either by SN2 reaction of an alkyl halide with cyanide ion or by dehydration of an amide. Nitriles undergo nucleophilic addition to the polar C=N bond in the same way that carbonyl compounds do. The most important reactions of nitriles are their hydrolysis to carboxylic acids, reduction to primary amines, and reaction with organometallic reagents to yield ketones. 

Beside these free radical reactions of sulfur dioxide, its electrophilic reactions generating sulfinates with organometallic compounds453,454 or sulfinic acids with arenes under Friedel-Crafts conditions455 are well known. To complete these three-component syntheses, the sulfinates prepared first are transformed to sulfones by reactions with appropriate electrophiles, discussed earlier in this chapter, i.e. equation 82. 

In general, the reaction can be performed only with organometallics of active metals such as lithium, sodium, and potassium, but Grignard reagents abstract protons from a sufficiently acidic C—H bond, as in R—C=C—H —> R—C=C—MgX. This method is best for the preparation of alkynyl Grignard reagents. ... 

The Conversion of Carboxylic Acid Salts to Ketones With Organometallic Compounds... 

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