198698-55-4Relevant academic research and scientific papers
Cross-coupling reaction of α-chloroketones and organotin enolates catalyzed by zinc halides for synthesis of γ-diketones
Yasuda, Makoto,Tsuji, Shoki,Shigeyoshi, Yusuke,Baba, Akio
, p. 7440 - 7447 (2002)
The reaction of tin enolates 1 with α-chloro- or bromoketones 2 gave γ-diketones (1,4-diketones) 3 catalyzed by zinc halides. In contrast to the exclusive formation of 1,4-diketones 3 under catalytic conditions, uncatalyzed reaction of 1 with 2 gave aldol-type products 4 through carbonyl attack. NMR study indicates that the catalyzed reaction includes precondensation between tin enolates and α-haloketones providing an aldol-type species and their rearrangement of the oxoalkyl group with leaving halogen to produce 1,4-diketones. The catalyst, zinc halides, plays an important role in each step. The carbonyl attack for precondensation is accelerated by the catalyst as Lewis acid and the intermediate zincate promotes the rearrangement by releasing oxygen and bonding with halogen. Various types of tin enolates and α-chloro and bromoketones were applied to the zinc-catalyzed cross-coupling. On the other hand, the allylic halides, which have no carbonyl moiety, were inert to the zinc-catalyzed coupling with tin enolates. The copper halides showed high catalytic activity for the coupling between tin enolates 1 and organic halides 7 to give γ,δ-unsaturated ketones 8 and/or 9. The reaction with even chlorides proceeded effectively by the catalytic system.
SYNTHESIS OF HOMOALLYLIC ALCOHOLS. PART 3. GENERALIZATION TO THE USE OF ESTER ENOLATES AND GRIGNARD REAGENTS AS NUCLEOPHILES
Barluenga, Jose,Alvarez, Flora,Concellon, Jose M.,Yus, Miguel
, p. 3265 - 3285 (2007/10/02)
The successive treatment of different α-chloro carbonyl compounds (1) with a lithium ester enolate (6), lithium aluminium hydride or deuteride and final lithiation with lithium powder leads, after acid hydrolysis, to the corresponding homoallylic alcohols
