Terminal Heck Vinylations of Chelating Vinyl Ethers

Terminal chelation‐controlled Heck vinylations of electron‐rich amino‐functionalized vinyl ethers were performed with high regioselectivity furnishing moderate to good isolated yields of the corresponding 1‐alkoxy‐1,3‐butadienes. DFT calculations support an amine‐palladium(II) coordination strength...

Full description

Saved in:
Bibliographic Details
Published in:Advanced synthesis & catalysis 2004-12, Vol.346 (13-15), p.1773-1781
Main Authors: Stadler, Alexander, von Schenck, Henrik, Vallin, Karl S. A., Larhed, Mats, Hallberg, Anders
Format: Article
Language:English
Subjects:
Chelating
Conversion
cycloaddition
DFT
Dimethyl
Heck reaction
Mathematical analysis
Microwaves
regioselectivity
Terminals
vinyl ether
Vinyl ethers
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Terminal chelation‐controlled Heck vinylations of electron‐rich amino‐functionalized vinyl ethers were performed with high regioselectivity furnishing moderate to good isolated yields of the corresponding 1‐alkoxy‐1,3‐butadienes. DFT calculations support an amine‐palladium(II) coordination strength reactivity/selectivity rationale, where the dimethylamino group was the preferred metal presenting functionality. Controlled microwave heating effectively accelerated these palladium‐catalyzed reactions and full conversion could be achieved within 30 minutes. Subsequent Diels–Alder reactions with dimethyl acetylenedicarboxylate under microwave irradiation resulted exclusively in partly aromatized bi‐ and tricyclic compounds by elimination of the aminoalkoxy group. Thus, the selected dimethylamino auxiliary both controlled the regiochemistry in the palladium‐catalyzed vinylation and was easily displaced in the aromatization process.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.200404184