Fluoride-catalyzed aldol reaction of ethyl trimethylsilyldiazoacetate with aldehydes leading to ethyl α-diazo-β-hydroxy esters and rhodium catalyzed decarboxylative rearrangement of diazo urethanes leading to β-amino acrylates

✍ Scribed by Shuji Kanemasa; Takahiro Araki; Toshio Kanai; Eiji Wada

• Publisher: Elsevier Science
• Year: 1999
• Tongue: French
• Weight: 254 KB
• Volume: 40
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(99)00933-8

✦ Synopsis

Ethyl trimethylsilyldiazoacetate reacts smoothly with a variety of aldehydes at 0 °C in the presence of a catalytic amount of tetrabutylammonium fluoride to produce adiazo-13-hydroxy esters in good to excellent yields. The resulting a-diazo-13-hydroxy esters can be stereoselectively transformed, by a sequence of carbamation with p-toluenesulfonyl isocyanate and rhodium(II)-induced decarboxylative rearrangement, to a-or ~-substituted ll-(p-toluenesulfonylamino)acrylates depending upon migration aptitude of the substituents derived from the aldehydes.