Keto Grignard Reagents. Intramolecular Reduction<sup>*1</sup>

Fuson, Reynold C.; Shachat, Norman

doi:10.1021/jo01362a023

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“…The carbonation of a bifunctional bromomagnesium enolate of 1,4-dimesitoylbutane gave 2,5-dimesitoyladipic acid in good yield (260). Under similar conditions the dimagnesium derivatives of 1,4-dibromobutane, 1,5-dibromopentane, and 1,6-dibromohexane were also shown (261) to give mainly the normal addition products.…”

Section: T H I S C O N T E N T Imentioning

confidence: 91%

Syntheses Of Alkylated Alkanedioic Acids

Diaper¹,

KUKSIS²

1959

Chem. Rev.

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example of such a synthesis is the conversion of 2-pentenal, through a Reformatsky condensation with ethyl -bromopropionate and oxalation of the unsaturated product, eventually to 2,6-dimethylsuberic acid (401).It has been shown that formates and oxalates may function as carbonyl components in a Reformatsky synthesis. Ethyl -bromoisobutyrate reacts with ethyl oxalate (569) and with ethyl formate (82), giving hydroxy esters which could be converted to 2,2-dimethylsuccinic and 2,2,4,4-tetramethyIglutaric acids, respectively.The application of the Reformatsky reaction to nitriles (154) leads to the formation of ketones in a manner comparable with the Grignard reaction and is a convenient method for the synthesis of /3-keto esters.By varying the nature of the carbonyl compounds and the halo esters employed, many alkylated dicarboxylic acids have been prepared with the help of this reaction, yet the possible products may be of only a few types. Branching is confined to the a-and ß-positions at one or both ends of the chain, and while the -position may bear one, two, or no alkyl groups, the /3-position cannot bear more than one side chain.Theoretically, in all of the above cases the ester groups of the final products may be converted into aldehyde or keto groups through the acyl chlorides and dialkyl metals (142).A repetition of the Reformatsky process would lengthen the chain with or without further branching at the new points of junction of carbon chains (629).

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Section: T H I S C O N T E N T Imentioning

confidence: 91%