Subject lithium halides

The boroxines could then be subjected to Suzuki coupling with aryl, vinyl, or benzyl halides. Suzuki coupling with tri- -butylstannyl chloride also gave the tri- -butylstannyl-substituted thiophenes 221. These can form the starting materials for further transformations. The carbonylative coupling with halides resulted in the formation of ketones tin-lithium exchange followed by reaction with electrophiles led to a host of other useful products (Scheme 65). 

Very recently, the preparation of zinc /3-diiminate derivatives became the subject of interest due to their catalytic activity in the copolymerization of CO2 with epoxidesd They can be prepared in high yields by direct reaction of the corresponding /3-ditmines with diaUcylzinc compounds or by treatment of the /3-diimine-lithium salts with zinc halide followed by an alkylation reaction (Scheme 9). 

In the laboratory of T.F. Jamison, the synthesis of amphidinolide T1 was accomplished utilizing a catalytic and stereoselective macrocyclization as the key step. ° The Myers asymmetric alkylation was chosen to establish the correct stereochemistry at the C2 position. In the procedure, the alkyl halide was used as the limiting reagent and almost two equivalents of the lithium enolate of the A/-propionyl pseudoephedrine chiral auxiliary was used. The alkylated product was purified by column chromatography and then subjected to basic hydrolysis to remove the chiral auxiliary. 

In studies concerned with optimization of the Suzuki cross-coupling of 2-pyridyl nucleophiles, lithium triisopropyl 2-pyridylborates are shown to be the most suitable boron coupling partners (eq 60). The borates are isolated and subjected to coupling with various aryl and hetaryl halides (X = Cl, Br) to give the corresponding azabiaryls. ... 

A direct route to the many naturally occurring 1,5-diene systems is the coupling of two allyl units. To the available methods for this procedure can be added the reaction of an allylic halide with an allyl-lithium generated in situ by reduction of a mesitoate ester of the corresponding allylic alcohol (437). Only the mesitoate-derived allylic portion is subject to the allylic... 

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