4491-45-6

Upstream product

• 197520-92-6 6-Methoxy-2,2-dimethyl-5-phenyl-[1,3]dioxin-4-one 
• 75-65-0 tert-butyl alcohol 
• 40710-05-2 1-(tert-butyl) 3-methyl 2-diazomalonate 
• 934-56-5 trimethyl(phenyl)stannane 
• 2996-92-1 phenyl trimethylsiloxane 
• 15231-78-4 2.2-dimethyl-5-phenyl-1,3-dioxane-4,6-dione 

Downstream Products

• 1133466-69-9 1-tert-butyl 3-methyl (S)-2-hydroxy-2-phenylmalonate 
• 1007121-13-2 (S)-1-tert-butyl 3-methyl 2-fluoro-2-phenylmalonate 

Relevant academic research and scientific papers

Rh(I)-catalyzed cross-coupling of α-diazoesters with arylsiloxanes

An Rh(I)-catalyzed cross-coupling of diazoesters with arylsiloxanes has been successfully achieved. This transformation is a new method for the construction of the C(sp3)-C(sp2) bond, thus providing an alternative synthesis of α-aryl esters. Rh(I)-carbene migratory insertion has been proposed to be involved in this coupling reaction. The reaction represents the first example of utilizing arylsiloxane as the coupling partner in the carbene-involved cross-coupling reactions.

RhI-Catalyzed Stille-Type Coupling of Diazoesters with Aryl Trimethylstannanes

A RhI-catalyzed cross-coupling of diazoester with arylstannane was developed. This reaction represents the first Stille-type coupling that uses a diazo compound as the coupling partner. The reaction is operationally simple and can be carried out under mild conditions, thus providing an alternative approach for the synthesis of α-aryl esters. RhI-carbene migratory insertion process is suggested to be involved as the key step in this Stille-type coupling.

An efficient method for generation of α-oxoketenes: Cycloreversion of enolized Meldrum's acid derivatives

A series of 6-methoxy- or siloxy-4H-1,3-dioxin-4-ones was synthesized from Meldrum's acids. These dioxinones underwent 4+2 cycloreversion to methoxy- or siloxycartbonylketenes and ketones quantitatively at 20-50°C. The ketenes were characterized by IR spectroscopy as well as by trapping with t-butanol. The ready cycloreversion of these enolized Meldrum's acid derivatives strongly indicates that the anomalously high susceptibility of Meldrum's acids to nucleophilic reagents is due to the participation of carboxyketenes generated through the cycloreversion of tautomeric 6-hydroxydioxinones.