On the impact of steric and electronic properties of ligands on gold(I)-catalyzed cycloaddition reactions.
It is shown that [4 + 3] and [4 + 2] cycloaddition pathways are accessible in the Au(I) catalysis of allene-dienes. Seven-membered ring gold-stabilized carbenes, originating from the [4 + 3] cycloaddition process, are unstable and can rearrange via a 1,2-H or a 1,2-alkyl shift to yield six- and seven-membered products. Both steric and electronic properties of the AuL(+) catalyst affect the electronic structure of the intermediate gold-stabilized carbene and its subsequent reactivity.
Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, USA.
Diego
D
Benitez
Ekaterina
E
Tkatchouk
Ana Z
AZ
Gonzalez
William A
WA
Goddard
F Dean
FD
Toste
D000466:Alkadienes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D006046:Gold / Q000737:chemistry*; D015394:Molecular Structure; D050607:Organogold Compounds / Q000737:chemistry*
D000466:Alkadienes; D050607:Organogold Compounds; C025947:propadiene; D006046:Gold