Oxonitriles: A Grignard Addition−Acylation Route to Enamides
- 23 September 2006
- journal article
- letter
- Published by American Chemical Society (ACS) in Organic Letters
- Vol. 8 (21) , 4903-4906
- https://doi.org/10.1021/ol0619765
Abstract
Sequential addition of three different Grignard reagents and pivaloyl chloride to 3-oxo-1-cyclohexene-1-carbonitrile installs four new bonds to generate a diverse array of cyclic enamides. Remarkably, formation of the C-magnesiated nitrile intermediate is followed by preferential acylation by pivaloyl chloride rather than consumption by an in situ Grignard reagent. Rapid N-acylation of the C-magnesiated nitrile generates an acyl ketenimine that reacts readily with Grignard reagents or a trialkylzincate, effectively assembling highly substituted, cyclic enamides.Keywords
This publication has 19 references indexed in Scilit:
- Cyclic Oxonitriles: Synergistic Juxtaposition of Ketone and Nitrile FunctionalitiesSynthesis, 2006
- Oxonitriles: Multicomponent Grignard Addition–AlkylationsAngewandte Chemie International Edition in English, 2004
- A modified Robinson annulation process to α,α-disubstituted-β,γ-unsaturated cyclohexanone system. Application to the total synthesis of nanaimoalTetrahedron, 2003
- Annulation routes to trans-decalinsTetrahedron, 1999
- Synthesis of macrocyclic enaminolactams by ring expansion reaction of 2-oxocyclododecane-1-carbonitrile with diarylcarbodiimidesTetrahedron, 1996
- Hydrocyanation of some α,β-unsaturated ketones, and the synthesis of some unusual isoxazolesJournal of the Chemical Society, Perkin Transactions 1, 1995
- Cycloalkylations ofN-(?-Halogenoalkyl)-substituted Macrocyclic ImidesHelvetica Chimica Acta, 1990
- Synthesis of macrocyclic imides by one‐step ring enlargementHelvetica Chimica Acta, 1989
- A new and facile perhydroazulene formation : the total synthesis of the carotane (+)-dauceneTetrahedron, 1987
- Photoaddition with 1,2-bis(trimethylsiloxy)cyclobutene: a versatile entry to the stereocontrolled total synthesis of various sesquiterpenes and diterpenesJournal of Photochemistry, 1985