Stabilization of reactive aldehydes by complexation with methylaluminum bis(2,6-diphenylphenoxide) and their synthetic application
Reactive aldehydes such as formaldehyde and alpha-chloro aldehydes can be successfully generated by treatment of readily available trioxane and alpha-chloro aldehyde trimers, respectively, with methylaluminum bis(2,6-diphenylphenoxide) (MAPH), and stabilized as their 1:1 coordination complexes with...
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Published in | Journal of the American Chemical Society Vol. 115; no. 10; pp. 3943 - 3949 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
Published |
WASHINGTON
American Chemical Society
01.05.1993
Amer Chemical Soc |
Subjects | |
Online Access | Get full text |
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Summary: | Reactive aldehydes such as formaldehyde and alpha-chloro aldehydes can be successfully generated by treatment of readily available trioxane and alpha-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 alpha-chloro aldehyde-MAPH complexes can be utilized as a stable source of gaseous formaldehyde and reactive alpha-chloro aldehydes, respectively, for the nucleophilic addition of various carbanions (organometallics, enolates, etc.). Formation of reactive aldehyde-MAPH complexes is firmly confirmed by H-1 NMR spectroscopy. A space-filling model of aldehyde-MAPH complexes implies that formaldehyde and alpha-chloro aldehydes coordinated with MAPH may be electronically stabilized by two parallel phenyl groups of aluminum ligands. |
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Bibliography: | istex:02AC86EB58847D269D099E7FAE210469BE8A68E7 ark:/67375/TPS-Q682N459-6 |
ISSN: | 0002-7863 1520-5126 |
DOI: | 10.1021/ja00063a013 |