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Tin for Organic Synthesis, 14 . Synthesis of Aromatic and α,β‐Unsaturated Aldehydes by a Friedel‐Crafts‐like Electrophilic Destannylation Using 1,1‐Dichloromethyl Methyl Ether
Author(s) -
Niestroj Michael,
Neumann† Wilhelm P.
Publication year - 1996
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19961290111
Subject(s) - chemistry , electrophile , aldehyde , friedel–crafts reaction , ether , electrophilic substitution , silyl ether , organic chemistry , silylation , medicinal chemistry , tin , reactivity (psychology) , catalysis , medicine , alternative medicine , pathology
A mild and effective method for the preparation of a variety of aromatic ( 7a–m ), heteroaromatic ( 7n–r ), and α,β‐unsaturated aldehydes ( 8a–f ) is described. The reaction of trialkylaryl‐ ( 2a–o ), heteroaryl‐ ( 2p–t ), and 1‐alkenylstannanes ( 4a–f and 5a–f ) with dichloromethyl methyl ether ( 1 , DCME) in the presence of aluminium trichloride followed by hydrolysis provides the corresponding aldehydes. In the case of arylstannanes the ipso ‐isomers are generally formed; the p ‐alde‐hydes occur as side products. The electrophilic substitution of 1‐alkenylstannanes with 1 leads to α,β‐unsaturated aldehydes in an ipso ‐ and stereospecific manner. A comparison of the leaving abilities of the stannyl and silyl groups shows a lower or even zero reactivity of the silyl‐substituted compounds 6a–c towards the electrophile 1 . In the silylstannylal‐kene 6c only the stannyl group reacts whereas the stannyl function remains unaffected in the product, aldehyde 11 .