Organolithium reagents, reaction with ketones

Reaction with Organolithium Reagents (Section 16.5B) Reactions of aldehydes and ketones with organolithium reagents are similar to those with Grignard reagents. 

Metallated tosylhydrazones react with aldehydes and ketones to afford /8-hydroxytosylhydrazones in good to excellent yield. Further reaction with organolithium reagent gives the corresponding homoallylic alcohol (Scheme... 

Reaction of organolithium reagents with aldehydes and ketones (Section... 

Reaction of organolithium reagents with aldehydes and ketones (Section 14.7) Organolithium reagents react with aldehydes and ketones in a manner similar to that of Grignard reagents to form alcohols. 

Cerium reagents have also been found to give improved yields in the reaction of organolithium reagents with carboxylate salts to give ketones. 

M. S. Jorgenson, "Preparation of Ketones from the Reaction of Organolithium Reagents with Carboxylic Acids, Organic Reactions 18, 1 (1970). 

Carbonyl- 4 C KIE in the reactions of ketones with organolithium reagents... 

M. J. Jorgenson, Preparation of ketones from the reaction of organolithium reagents with carboxylic acids, Org. React. 1970,18, 1-9. 

Reactions of either Grignard or organolithium reagents with most aldehydes, ketones, or esters produce alcohols. Reactions of organolithium reagents with carboxylic acids, or of Grignard reagents with nitriles, produce ketones. 

With organolithium reagents, stable intermediates are produced by addition to a carboxylic acid. On workup, these intermediates produce ketones. As with Grignard reagents, the reaction of organolithium reagents with esters produces tertiary alcohols because the intermediates decompose to ketones under the reaction conditions. The mechanisms for these processes are illustrated in the examples that follow. 

Chiral boronic esters react with organolithium reagents to form diorganylalkoxyboranes (borinic esters). Subsequent reaction with the anion of dichloromethyl methyl ether then yields chiral ketones by rearrangement of both of the groups on boron (Scheme 42). No racemization is observed in this sequence and alkyl-, aryl- or alkynyl-lithium reagents can be used. 

---