ISSN:
0009-2940
Keywords:
Pyrroles, heteroannulated
;
α-Pyridones, heteroannulated
;
Pentalenes, dihetero-
;
Nitrones
;
Heterocyclizations, 1,7-dipolar
;
Diels-Alder reactions
;
Singlet oxygen
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A Novel Route to Isoannulated Heteroaroamtic Compounds, 2[1]. - The Dipole Route to Furo/Thieno Pyrroles and α-Pyridones, and Their Benzo DerivativesA new methodology involving 1,7-dipolar cyclizations of conjugated dipoles followed by a multistep rearrangement affording ring-contracted products has been employed for the synthesis of various examples of the title compounds. Under different thermolysis conditions the annulated alkynyl nitrones 15-19, 45, and 46 are converted into isoannulated pyrroles and α-pyridones, respectively, with yields up to 90% (general reaction A → B + C). The product distribution is strongly influenced by the nature of the terminal substituent R, hence supporting a mechanism with oxo carbenes as central intermediates which undergo either 6-π cyclization to the pyrrole systems or Wolff rearrangement leading to conjugated ketenes, the precursors of the observed α-pyridones (see Scheme 1). Diels-Alder reactions were performed with benzofuropyridone 40a, napthopyridone 62 as well as with the corresponding dihydronaphtho compounds 64a, b. Whereas the tert-butyl derivatives 22b, 23b and 41b are rather unreactive against dienophiles, they are easily transformed into the cyclic imides 31, 32 and 52, respectively, under the influence of oxygen and light suggesting the formation and subsequent [4 + 2] cycloaddition of 1O2 as important steps.
Additional Material:
5 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19941270135
Permalink
