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Rhodium(II)‐Catalyzed Decomposition of β,γ‐Unsaturated Diazo Compounds
Author(s) -
Motallebi Shahrokh,
Müller Paul
Publication year - 1993
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.19930760806
Subject(s) - chemistry , diazo , intramolecular force , rhodium , decomposition , catalysis , wolff rearrangement , medicinal chemistry , insertion reaction , stereochemistry , organic chemistry
The Rh II ‐catalyzed decomposition of β,γ‐unsaturated diazo ketones 1 in the presence of MeOH leads via vinylogous Wolff rearrangement to γ,δ‐unsaturated esters 6 ( Schemes 1 and 2 ). A modest asymmetric induction is achieved when the reaction is carried out with chiral tetrakis(pyrrolidinecarboxylato)‐ or tetrakis(oxazolidinonato)dirhodium(II) complexes. Vinyl and phenyl diazoacetates 11 and 20 , respectively, or 1‐diazo‐3‐phenyl‐propan‐2‐one ( 25 ), when subjected to the same reaction conditions, react by OH insertion with MeOH ( Schemes 3–5 ). In the absence of MeOH, phenyl diazoacetates 20 and 25 undergo intramolecular CH insertion to 22 and 26 , respectively. Intramolecular CH insertion occurs with N ‐aryldiazoamides 23 even in the presence of MeOH ( Scheme 5 ).