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[CpRu]‐Catalyzed Carbene Insertions into Epoxides: 1,4‐Dioxene Synthesis through S N 1‐Like Chemistry with Retention of Configuration
Author(s) -
Achard Thierry,
Tortoreto Cecilia,
PobladorBahamonde Amalia I.,
Guénée Laure,
Bürgi Thomas,
Lacour Jérôme
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201402994
Subject(s) - carbene , deoxygenation , chemistry , catalysis , ring (chemistry) , walden inversion , diazo , stereochemistry , atom (system on chip) , metal , medicinal chemistry , organic chemistry , computer science , embedded system
Rather than lead to the usual deoxygenation pathway, metal carbenes derived from α‐diazo‐β‐ketoesters undergo three‐atom insertions into epoxides using a combination of 1,10‐phenanthroline and [CpRu(CH 3 CN) 3 ][BAr F ] as the catalyst. Original 1,4‐dioxene motifs are obtained as single regio‐ and stereoisomers. A perfect syn stereochemistry (retention, e.r. up to 97:3) is observed for the ring opening, which behaves as an S N 1‐like transformation.