Ketones synthesis from organolithium reagents

Synthesis of ketones and aldehydes from acid chlorides (or esters) via reaction of N-methoxy-N-methylamides with a Grignard or organolithium reagent (see 1 edition). 

A regioselective synthesis of 1,4-dienes (69) from a,/3,7,5-unsaturated ketones, e.g. (68), proceeds in excellent yield on alkylation with organolithium reagents followed by reduction with lithium in liquid ammonia. The reaction is not successful with the corresponding aldehydes and the lithamide reduction product must be quenched with ethanol or t-butyl alcohol rather than with conventional protic sources such as ammonium chloride. Where applicable, the 1,4-diene is formed as a mixture of the E- and Z-stereoisomers at the newly developed double bond. 

The synthesis of ketones from acid chlorides has been demonstrated with several organometallic reagents (see Sections 1.13.3,1.13.4 and 1.13.5) however, the acylation of organolithiums often leads to substantid amounts of overaddition product. Initially, acid chlorides appear to be a poor choice for... 

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