Base cleavage of .beta.,.gamma.-unsaturated bicyclic cyclobutanones

Synthesis of Alkali Metal Carboxylates and Carboxylic Acids Using “Wet” and “Anhydrous” Alkali Metal Hydroxides

“…Successful C,C bond scission by “APH” has been also disclosed for other enolizable ketones such as the bicyclo[2.2.2]cyclooctanone 316 (Scheme , entry a) and for compounds 39 (Scheme , entry d), 117 (Scheme , entry c), and 318 (Scheme , entry c) bearing an enolizable cyclobutanone substructure. Metalation, however, occurs as already stressed on 115a and 115b (Scheme , entries a,b) possessing closely related structures …”

“…Related reactions have been successfully achieved using “APH” generated from potassium hydride and a stoichiometric amount of water (Scheme , entry c, Scheme , entry c), , and therefore the role of the excess of potassium t -butoxide and of the t -butanol produced in situ by reaction of water on potassium t -butoxide in the scission reaction is questionable…”

“…It has been also described that “APH” allows the cleavage of (i) the α-phenylsulfanyl-cyclobutanone 39 (Scheme , entry d), which neither sodium hydroxide nor sodium methylate is able to achieve even under more drastic conditions (Scheme , entries b,c), and (ii) the α,α-dimethyl cyclobutanone 318 fused to the cyclopentene ring, to the mixture of isomeric cyclopentenecarboxylic acids whose α-carbon is fully alkyl-substituted 319 (Scheme , entry c) under milder conditions and in better yield than when potassium hydroxide pellets in anhydrous or aqueous methanol are instead used (Scheme , compare entry c to entries a,b) …”

“…Similarly, “APH” cleaves the cyclobutanone present in the bicyclo[3.1.1]cyclohexanone 303 (Scheme , entries c−e) under milder conditions than potassium pellets (Scheme , entries a,b, as compared to entries c−e) and more efficiently than using “anhydrous potassium hydroxide” prepared from potassium hydride instead (Scheme , entry c, as compared to entries d,e) …”

Rhodium-Catalyzed Hydroallylation of Activated Alkenes

“…The products 9a , 10a , , 18a , 24a , ,25a 26a , ,25b,c 28a , 29a , ,25a,d and 3 2a 8,25c-f were characterized by comparing their spectral data to those reported in the literature.…”