130199-70-1Relevant articles and documents
Stabilization of reactive aldehydes by complexation with methylaluminum bis(2,6-diphenylphenoxide) and their synthetic application
Maruoka, Keiji,Concepcion, Arnel B.,Murase, Noriaki,Oishi, Masataka,Hirayama, Naoki,Yamamoto, Hisashi
, p. 3943 - 3949 (2007/10/02)
Reactive aldehydes such as formaldehyde and α-chloro aldehydes can be successfully generated by treatment of readily available trioxane and α-chloro aldehyde trimers, respectively, with methylaluminum bis(2,6-diphenylphenoxide) (MAPH), and stabilized as their 1:1 coordination complexes with MAPH. The resulting CH2=O·MAPH complex reacts with a variety of olefins to furnish ene-reaction products with excellent regio- and stereoselectivities. In addition, this complex as well as α-chloro aldehyde-M APH complexes can be utilized as a stable source of gaseous formaldehyde and reactive α-chloro aldehydes, respectively, for the nucleophilic addition of various carbanions (organometallics, enolates, etc.). Formation of reactive aldehyde-MAPH complexes is firmly confirmed by 1H NMR spectroscopy. A space-filling model of aldehyde-M APH complexes implies that formaldehyde and α-chloro aldehydes coordinated with MAPH may be electronically stabilized by two parallel phenyl groups of aluminum ligands.