144536-58-3

Upstream product

• 6651-36-1 1-(Trimethylsilyloxy)cyclohexene 
• 17510-46-2 3,3-dimethyl-2-(trimethylsilyl)oxy-1-butene 
• 17851-97-7 1-tri(n-butyl)stannyloxy-1-cyclohexene 
• 5469-26-1 1-Bromopinacolon 
• 17795-68-5 (C₄H₉)3SnOC(t-C₄H₉)CH₂ 
• 822-87-7 2-Chlorocyclohexanone 
• 141792-49-6 N-(1-Bromo-3,3-dimethyl-2-butylidene)isopropylamine 
• 141792-47-4 N-(1-Chloro-3,3-dimethyl-2-butylidene)isopropylamine 
• 13547-70-1 1-chloro-3,3-dimethyl-butan-2-one 

Relevant academic research and scientific papers

Cross-coupling reaction of α-chloroketones and organotin enolates catalyzed by zinc halides for synthesis of γ-diketones

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.

NMR Studies of Five-Coordinate Tin Enolate: An Efficient Reagent for Halo Selective Reaction toward α-Halo Ketone or α-Halo Imine

NMR studies of tin enolates 1, in the presence of HMPA, revealed the presence of a five-coordinate O-stannyl enolate 1(h) which contributes to upfield shifts of Sn peaks in the 119Sn NMR spectrum and increased coupling constants J(119Sn-13C), compared wit

Oxovanadium-Induced Oxidative Desilylation for the Selective Synthesis of 1,4-Diketones

Silyl enol ethers underwent the VO(OR)Cl2-induced homo- or cross-coupling giving 1,4-diketones selectively via one-electron oxidative desilylation.

PALLADIUM OR RUTHENIUM CATALYZED REACTION OF Α-HALO KETONES WITH TRIBUTYLTIN ENOLATES: PREPARATION OF UNSYMMETRICAL 1,4-DIKETONES

Palladium or ruthenium catalyzed cross-coupling of α-halo ketones with tributyltin enolates gave unsymmetrical 1,4-diketones.The method was applied to the dihydrojasmone synthesis.