Generation of stoichiometric ethylene and isotopic derivatives and application in transition-metal-catalyzed vinylation and enyne metathesis.
Ethylene is one of the most important building blocks in industry for the production of polymers and commodity chemicals. (13)C- and D-isotope-labeled ethylenes are also valuable reagents with applications ranging from polymer-structure determination, reaction-mechanism elucidation to the preparation of more complex isotopically labeled compounds. However, these isotopic derivatives are expensive, and are flammable gases, which are difficult to handle. We have developed a method for the controlled generation of ethylene and its isotopic variants including, for the first time, fully isotopically labeled ethylene, from simple alkene precursors by using Ru catalysis. Applying a two-chamber reactor allows both the synthesis of ethylene and its immediate consumption in a chemical transformation permitting reactions to be performed with only stoichiometric amounts of this two carbon olefin. This was demonstrated in the Ni-catalyzed Heck reaction with aryl triflates and benzyl chlorides, as well as Ru-mediated enyne metathesis.
Center for Insoluble Protein Structures (inSPIN), Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000 Aarhus C (Denmark), Fax: (+45) 4189 3001.
Geanna K
GK
Min
Klaus
K
Bjerglund
Søren
S
Kramer
Thomas M
TM
Gøgsig
Anders T
AT
Lindhardt
Troels
T
Skrydstrup
D002247:Carbon Isotopes / Q000737:chemistry; D002384:Catalysis; D003903:Deuterium / Q000737:chemistry; D005030:Ethylenes / Q000737:chemistry*; D007553:Isotope Labeling; D009532:Nickel / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry
D002247:Carbon Isotopes; D005030:Ethylenes; D014753:Vinyl Compounds; D009532:Nickel; D012428:Ruthenium; C036216:ethylene; D003903:Deuterium
Heck reaction; deuterium; ethylene; isotopic labeling; metathesis