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Controlled Allylic Transformations via the Meisenheimer Rearrangement
Author(s) -
Rautenstrauch Valentin
Publication year - 1973
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.19730560731
Subject(s) - chemistry , allylic rearrangement , hydroxylamine , ketone , alcohol , amine gas treating , allyl alcohol , allylic alcohol , sequence (biology) , medicinal chemistry , methylation , primary (astronomy) , ethanol , stereochemistry , organic chemistry , biochemistry , physics , astronomy , gene , catalysis
Described are synthetic sequences which effect allylic transformations I and II. Sequence I involves (1) conversion of a primary allyl alcohol into the corresponding N, N‐dimethyl‐amine oxide, (2) [2,3]‐rearrangement to give an N, N‐dimethylhydroxylamine and (3a) reduction to give the ‘rearranged’ secondary or tertiary allyl alcohol [ e.g. 36 → 35 → 37 → 40 ]. Sequence II involves the same steps (1) and (2), followed by (3b) N‐methylation of a secondary N, N‐dimethyl‐hydroxylamine and (4) Hofmann elimination to give a vinyl ketone [ e.g . 11 → 12 → 13 → 14 → 15 ].