82562-01-4

Upstream product

• 15435-71-9 sodium acetylacetonate 
• 2142-63-4 1-(3-Bromophenyl)ethanone 
• 123-42-2 4-Hydroxy-4-methyl-2-pentanone 
• 67-64-1 acetone 
• 99-02-5 3'-Chloroacetophenone 

Relevant academic research and scientific papers

C-C Activation by Retro-Aldol Reaction of Two β-Hydroxy Carbonyl Compounds: Synergy with Pd-Catalyzed Cross-Coupling to Access Mono-α-arylated Ketones and Esters

A retro-aldol reaction of two β-hydroxy compounds in synergy with Pd-catalyzed cross-coupling of aryl halides is reported herein, which produces selectively mono-α-arylated ketones and esters in good yields. This reaction is compatible with a broad range of aryl iodides, bromides, chlorides, and triflates and can tolerate an array of functional groups on the aromatic ring. Ready scale-up of this reaction to gram level is applicable without an appreciable decrease in the reaction yield. Furthermore, concise syntheses of biologically active isocoumarin and indole derivatives have been achieved to greatly demonstrate the synthetic value of this retro-aldol reaction. Finally, the reaction mechanism has been discussed on the basis of experimental observations and DFT computational results. A regulated six-membered-ring transition structure has been located for the key retro-aldol C-C cleavage, which constitutes the rate-determining step of a full catalytic cycle. The concept of C-C activation by retro-aldol reaction may also find applications in other fundamental reactions.

Nickel-Catalyzed Mono-Selective α-Arylation of Acetone with Aryl Chlorides and Phenol Derivatives

The challenging nickel-catalyzed mono-α-arylation of acetone with aryl chlorides, pivalates, and carbamates has been achieved for the first time. A nickel/Josiphos-based catalytic system is shown to feature unique catalytic behavior, allowing the highly selective formation of the desired mono-α-arylated acetone. The developed methodology was applied to a variety of (hetero)aryl chlorides including biologically relevant derivatives. The methodology has been extended to the unprecedented coupling of acetone with phenol derivatives. Mechanistic studies allowed the isolation and characterization of key Ni0 and NiII catalytic intermediates. The Josiphos ligand is shown to play a key role in the stabilization of NiII intermediates to allow a Ni0/NiII catalytic pathway. Mechanistic understanding was then leveraged to improve the protocol using an air-stable NiII pre-catalyst.

Preparation of a highly congested carbazoyl-derived p,n-type phosphine ligand for acetone monoarylations

We report a newly developed carbazoyl-derived P,N-type phosphine ligand (L1) for the monoarylation of acetone with aryl chlorides. The proposed Pd(dba)2/L1 catalyst exhibited remarkable catalytic reactivity toward highly electron rich and sterically congested aryl chlorides, with catalyst loading as low as 0.1 mol % of Pd along with excellent chemoselectivity. A reaction rate study of the system using electronically diverse aryl chlorides determined the mechanisms regarding the rate-limiting steps in this reaction. The oxidative addition adduct of Pd-PhenCar-Phos with p-chlorotoluene showed the participation of N-Pd coordination in the metal complex. The isolated palladium complex C1 could be utilized as a precatalyst in the transformation and achieved performance comparable to that of the in situ generated palladium species.

A VERSATILE SYNTHESIS OF ARYLACETONES FROM ARYL HALIDES AND ACETYLACETONATE

Reaction of aryl halides with sodium or potassium acetylacetonate in the presence of a copper catalyst affords directly arylacetones resulted from deacetylation of initially formed 3-arylacetylacetones in good yields.