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Captodative olefins in normal and inverse Diels ‐ Alder Reactions
Author(s) -
Mertes Jürgen,
Mattay Jochen
Publication year - 1988
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19880710408
Subject(s) - methacrolein , chemistry , methyl vinyl ketone , acrylonitrile , cyclopentadiene , reactivity (psychology) , ketone , methyl acrylate , organic chemistry , acrolein , medicinal chemistry , catalysis , copolymer , polymer , medicine , alternative medicine , pathology , methacrylic acid
Olefins with captodative substitution are reactive dienophiles in Diels ‐ Alder reactions with normal and inverse electron demand. This is shown for reactions of 2‐( tert ‐butylthio)acrylonitrile ( 1 ) with various dienes and heterodienes, e.g. 1,3‐cyclohexadiene, hexachloro‐1, 3‐cyclopentadiene, acrolein, methacrolein, and methyl vinyl ketone ( Schemes 2 and 3 ). In case of the hetrodienes, 3,4‐dihydro‐ 2H ‐pyrans are formed beside small amounts of tetrahydrothiophenes; however, with methyl vinyl ketone, both reaction pathways are equally followed. The high reactivity of captodative olefins in Diels ‐ Alder reactions are rationalized on the basis of Sustmann 's FMO model under consideration of Viehe's concept of captodative substitution of alkenes.