Organolithium reagents oxidation

Section 15 4 Grignard and organolithium reagents react with ethylene oxide to give primary alcohols... 

During addition of an ethereal solution of deuterium oxide (containing some peroxide) to a suspension of the organolithium reagent in pentane, a violent explosion occurred. This may have been initiated by the peroxide present, but probably... 

Scheme 2.38 Functionalized allenes formed by 1,4-addition of organolithium reagents to enynes and electrophilic trapping with aldehydes (111, 112) ketones (113,114), ethylene oxide (115) and carbon dioxide (116).

Some reports concerning the reaction of lithiated thioallylethers with oxiranes have been published. A slow reaction was observed with a terminal oxirane. However, with cyclopentadiene oxide, the reaction occured smoothly with an excellent regioselectivity in favor of the Sjv2 displacement in the ally lie position. Other examples involving sulfur, selenium and silicon stabilized organolithium reagents have been reported . 

A method for oxidative cleavage of cyclic ketones involves a four-stage process. First, the ketone is converted to an a-phenylthio derivative (see Section 4.7). The ketone is then converted to an alcohol, either by reduction or addition of an organolithium reagent. This compound is then treated with lead tetraacetate to give an oxidation... 

Conjugate addition to a, -unsaturated esters.1 The unsaturated esters of this phenol undergo ready conjugate addition with a variety of organolithium reagents, with t-butyllithium providing the only exception. The adducts are oxidatively hydrolyzed to carboxylic acids by CAN (10, 162). 

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