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 inJournal of the American Chemical Society Vol. 115; no. 10; pp. 3943 - 3949
Main Authors Maruoka, Keiji, Concepcion, Arnel B, Murase, Noriaki, Oishi, Masataka, Hirayama, Naoki, Yamamoto, Hisashi
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 01.05.1993
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Exact sciences and technology
Organic chemistry
Physical Sciences
Science & Technology
KETONES
ORGANO-ALUMINUM REAGENTS
ENOL ETHERS
ANTI-CRAM
CARBONYL ALKYLATION
OBTAINING UNUSUAL EQUATORIAL
FURAN ANNELATION
RABBIT MUSCLE ALDOLASE
ALLYL VINYL ETHERS
CLAISEN REARRANGEMENT
Stereoselectivity
Complexation
Haloaldehyde
Regioselectivity
Ene reaction
Aluminium Organic compounds
Aldehyde
Ethylenic compound
Formaldehyde
Nucleophilic addition
Primary alcohol
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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.
Bibliography:istex:02AC86EB58847D269D099E7FAE210469BE8A68E7
ark:/67375/TPS-Q682N459-6
ISSN:0002-7863
1520-5126
DOI:10.1021/ja00063a013