Diethylaluminum amides

As a further application of the reaction, the conversion of an endocyclic double bond to an c.xo-methylene is possible[382]. The epoxidation of an cWo-alkene followed by diethylaluminum amide-mediated isomerization affords the allylic alcohol 583 with an exo double bond[383]. The hydroxy group is eliminated selectively by Pd-catalyzed hydrogenolysis after converting it into allylic formate, yielding the c.ro-methylene compound 584. The conversion of carvone (585) into l,3-disiloxy-4-methylenecyclohexane (586) is an example[382]. 

Overman and Flippin utilized diethylaluminum amides for facile aminolysis of epoxides [71], The procedure involved treating a primary or secondary amine in CH2CI2 with EtsAl (1 equiv.) at room temperature for 30 min, then reaction with epoxide (1 equiv.) overnight. Hydrolysis of the resulting amino aluminate eventually afforded the /8-amino alcohol product in good yield. Aminolysis of cyclopentene oxide with diethylaluminum anilide is shown in Sch. 43 as a typical example. 

Conversion of amines into metal amides is an alternative method to facilitate the oxirane ring opening. The metal amides used are, for example, diethylaluminum amides, trimethylsilylamides and halo-magnesium amides. ... 

Diethylaluminum amide was prepared by bubbling ammonia through a toluene solution of tri-ethyMuminum [8] and tris-ethylaminoborane was syntheazed by the reaaion of BQ3 rvith EtNH2... 

Among other reagents that effect epoxide ring opening are diethylaluminum 2,2,6,6-tetramethylpiperidide and magnesium (V-cyclohexyl-A-O -propy amide. 

Organoaluminum compounds also undergo insertion reaction with isocyanates. For example, aluminum trialkyls react with alkyl and aryl isocyanates to give carboxylic acid amides after hydrolysis . Alkyl aluminum chlorides react similarly . Aluminium trichloride also forms insertion products with isocyanates Diethylaluminum ethyl thiolate or dimethylamide react with equimolar amounts of alkyl or aryl isocyanates to give the expected insertion products 274. ... 

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