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Stereoselective Peterson Olefinations from Bench‐Stable Reagents and N ‐Phenyl Imines
Author(s) -
Das Manas,
Manvar Atul,
Jacolot Maïwenn,
Blangetti Marco,
Jones Roderick C.,
O'Shea Donal F.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500475
Subject(s) - stereoselectivity , electrophile , trimethylsilyl , chemistry , aniline , organic chemistry , medicinal chemistry , substrate (aquarium) , reagent , amine gas treating , catalysis , oceanography , geology
The synthesis of bench‐stable α,α‐bis(trimethylsilyl)toluenes and tris(trimethylsilyl)methane is described and their use in stereoselective Peterson olefinations has been achieved with a wide substrate scope. Product stereoselectivity was poor with carbonyl electrophiles ( E / Z ∼1:1 to 4:1) though this was significantly improved by employing the corresponding substituted N ‐benzylideneaniline (up to 99:1) as an alternative electrophile. The olefination byproduct was identified as N , N ‐bis(trimethylsilyl)aniline and could be easily separated from product by aqueous acid extraction. Evidence for an autocatalytic cycle has been obtained.