Highly Efficient Peterson Olefination Leading to Unsaturated Selenoamides and Their Characterization
- 26 July 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 68 (21) , 7979-7982
- https://doi.org/10.1021/jo034653k
Abstract
The Peterson olefination of aromatic aldehydes with an α-silyl selenoacetamide proceeded smoothly with high stereoselectivity to give E-α,β-unsaturated selenoamides in good to high yields. The reaction with aldehydes bearing alkenyl and dienyl groups gave the corresponding selenoamides bearing dienyl and trienyl groups, but the stability of the products depended on the substituents on the aromatic ring. X-ray molecular analysis disclosed that the α,β,γ,δ-unsaturated selenoamides had a nearly planar structure. In the 77Se NMR spectra, signals were observed in the region greater than 130 ppm depending on the substituents on the aromatic ring, whereas the 1J coupling constant between the carbon atom and the selenium atom was almost independent of the substituents. A linear relationship was observed between the chemical shifts in the 77Se NMR spectra and Hammet σ parameters, and this correlation was retained even when one or two alkenyl groups were introduced to α,β-unsaturated selenoamides, although it became less sensitive.Keywords
This publication has 33 references indexed in Scilit:
- Diastereoselective Michael Addition of Organolithium Reagents to Chiral α,β-Unsaturated SelenoamideSynlett, 1998
- Syntheses of Selenothioic and Diselenoic Acid EstersSulfur reports, 1998
- Structure of N-Aryl Selenoacetamides in Solutions and in the Solid StateThe Journal of Organic Chemistry, 1998
- An Efficient Synthetic Method of Aliphatic Selenoamides via Selenoketene IntermediatesSynlett, 1996
- Highly efficient one-pot synthesis of α,α-disubstituted selenoamides and their first reduction to aminesChemical Communications, 1996
- Übergangsmetall-koordinierte heteroalkene als synthesebausteine: Nachweis und charakterisierung einer zwischenstufe der reaktion von thio- und selenoaldehyd-komplexen mit bis(diethylamino)acetylenJournal of Organometallic Chemistry, 1990
- Übergangsmetall‐koordinierte Heteroolefine als Synthesebausteine: Thio‐ und Selenoacrylamide aus 1‐(Diethylamino)‐1‐propin und Heteroaldehyd‐ und ‐keton‐KomplexenEuropean Journal of Inorganic Chemistry, 1988
- Side-chain13C nuclear magnetic resonance shifts in ring-substituted styrenes. The effect of β-substituents on β-carbon shiftsJournal of the Chemical Society, Perkin Transactions 2, 1988
- Thio- and seleno-acrylamide derivatives from ynamines and transition metal-co-ordinated thio- and seleno-aldehydes and -ketonesJournal of the Chemical Society, Chemical Communications, 1987
- Selenium-77 NMR studies of some organoselenium compounds containing-selenium double bondsJournal of the American Chemical Society, 1981