Diisopropylaminomagnesium bromide

Treatment of cyclic ketones with [(-)-menthyl] (A)-4-methylbenzenesulfinate in the presence of diisopropylaminomagnesium bromide affords optically active a-sulfinylcycloalkanones 1 as diastereomeric mixtures. This reaction is accompanied by complete inversion of configuration at sulfur and generation of a new stereogenic center at the a-carbon atom71. 

One of these important bases, diisopropylaminomagnesium bromide, was first introduced by Frostick and Hauser in 1949 as a catalyst for the Claisen condensation. However, the most generally useful base has turned out to be lithium diisopropylamide (LDA), which was first used by Hamell and Levine for the same purpose in 1950 (equation 3). After the introduction of LDA, it was more than 10 years before it was used by Wittig for the stoichiometric deprotonation of aldimines in what has come to be known as the Wittig directed aldol condensation.In a seminal paper in 1970, Rathke reported that the lithium enolate of ethyl acetate is formed by reaction of the ester with lithium hexamethyldisilazane in THF. - Rathke found that THF solutions of the lithium enolate are stable indefinitely at -78 °C, and that the enolate reacts smoothly with aldehydes and ketones to give p-hydroxy esters (equation 4). 

Diisopropylaminomagnesium bromide /J-Keto-y-lactones (tetronic acids) from a-acoxycarboxylic acid esters... 

A mixture of d-thiolvalerolactone and diethyl oxalate added dropwise with ice-salt-cooling at —10 to 5 to an ethereal suspension of diisopropylaminomagnesium bromide (prepared by adding a soln. of diisopropylamine in abs. ether to ethereal ethylmagnesium bromide), and stirred 12 hrs. at room temp. a-ethoxalyl-5-thiolvalerolactone (startg. m. f. 647). Y 74%. F. e. s. F. Korte and K.H.Biichel, B,93, 1021 (1960). 

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