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Copper(I)‐ and Copper(II)‐catalyzed Diels ‐ Alder Additions of α‐Substituted Acrylonitrile to Furan. The Synthesis of 7‐Oxa‐bicyclo[2.2.1]hept‐5‐en‐2‐one
Author(s) -
Vieira Eric,
Vogel Pierre
Publication year - 1982
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.19820650604
Subject(s) - chemistry , furan , acrylonitrile , saponification , bicyclic molecule , adduct , catalysis , copper , hydrolysis , medicinal chemistry , malononitrile , ketone , organic chemistry , copolymer , polymer
The difficult Diels ‐ Alder additions of α‐acetoxy‐ and α‐chloroacrylonitrile to furan can be run at 20–35° and atmospheric pressure in the presence of CuCl. Cu(BF 4 ) · 6 H 2 O, Cu(OOCCH 3 ) 2 · H 2 O or cupric tartrate · 3H 2 O. Under kinetic control, the exo ‐carbonitrile adducts 2 and 8 , respectively, are favoured. Saponification of the 2endo ‐acetoxy‐7‐oxabicyclo[2.2.1]hept‐5‐ene‐2 exo ‐carbonitrile ( 2 ) furnished the 7‐oxabicyclo[2.2.1]hept‐5‐en‐2‐one ( 4 ). Basic hydrolysis of the adducts ( 8 + 9 ) of α‐chloroacrylonitrile to furan and its 5 exo , 6 exo ‐isopropylidenedioxy derivatives did not give the corresponding ketones, the carboxamides 14 + 15 and 16 + 17 , respectively, were isolated.