172467-95-7Relevant articles and documents
Generation of magnesium alkylidene carbenoids from 1-halovinyl sulfoxides with Grignard reagent - Their property and some synthetic uses
Satoh,Takano,Someya,Matsuda
, p. 7097 - 7100 (1995)
The first example of magnesium alkylidene carbenoids is described. 1-Halovinyl sulfoxides 3 (X = F, Cl, Br) were synthesized from ketones and aryl halomethyl sulfoxides in three steps in moderate to good overall yields. Ligand exchange reaction of the sulfoxides of 3 with ethylmagnesium halide in THF at low temperature afforded a magnesium alkylidene carbenoid, which reacted with several electrophiles to give new alkylidene compounds.
Magnesium alkylidene carbenoids: Generation from 1-halovinyl sulfoxides with Grignard reagents and studies on their property, mechanism, and some synthetic uses
Satoh, Tsuyoshi,Takano, Koji,Hiroyuki, Ota,Someya, Hideaki,Matsuda, Kenji,Koyama, Mai
, p. 5557 - 5574 (2007/10/03)
Magnesium alkylidene carbenoids were generated from 1-halovinyl sulfoxides, derived from ketones and aryl halomethyl sulfoxide, through the ligand exchange reaction of sulfoxides with Grignard reagents. The generated magnesium alkylidene carbenoids were found to be stable at -78 °C for over 30 min. The carbenoids reacted with aldehydes to give the adducts in moderate yields; however, they were found to be relatively unreactive to usual electrophiles. The generated magnesium alkylidene carbenoid exists in equilibrium between an α-halo alkenyl Grignard reagent and an alkylidene carbene-magnesium halide complex. Halogen exchange and geometrical isomerization of the alkylidene carbenoids were observed. 1-Chlorovinyl sulfoxides reacted with excess aryl Grignard reagents to give alkenyl Grignard reagents having an aryl group. These Grignard reagents reacted with several electrophiles to give tetra-substituted olefins in moderate to good yields.
