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Radikalinduzierte intramolekulare 1, 4‐Verschiebung einer Formylgruppe
Author(s) -
Kalvoda Jaroslav,
Grob JÜRgen
Publication year - 1978
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.19780610608
Subject(s) - chemistry , intramolecular force , aldehyde , intramolecular reaction , stereochemistry , photodissociation , radical , medicinal chemistry , ketene , photochemistry , organic chemistry , catalysis
Radical‐induced Intramolecular 1,4‐Transfer of a Formyl Group A further example of a radical‐induced intramolecular shift of a functional group in steroids is described. In analogy to the sequence leading to the 1, 4‐transfer of cyano groups [3], 11 β‐nitrite photolysis was used to generate the appropriate C (18) radical in the 20‐hydroxy‐11 β‐nitrosyloxy‐pregnene‐21‐al 6 . Intramolecular addition of the radical center to the double‐bond of the specially adjacent aldehyde function, followed by fragmentation of the intermediate cyclic alkoxy radical and subsequent oxidation lead directly to the rearranged 18‐formyl compound 10 .