Manganese catalyzed cis-dihydroxylation of electron deficient alkenes with H(2)O(2).
A practical method for the multigram scale selective cis-dihydroxylation of electron deficient alkenes such as diethyl fumarate and N-alkyl and N-aryl-maleimides using H(2)O(2) is described. High turnovers (>1000) can be achieved with this efficient manganese based catalyst system, prepared in situ from a manganese salt, pyridine-2-carboxylic acid, a ketone and a base, under ambient conditions. Under optimized conditions, for diethyl fumarate at least 1000 turnovers could be achieved with only 1.5 equiv. of H(2)O(2) with d/l-diethyl tartrate (cis-diol product) as the sole product. For electron rich alkenes, such as cis-cyclooctene, this catalyst provides for efficient epoxidation.
Saisaha
Pattama
P
Stratingh Institute for Chemistry, Faculty of Mathematics and Natural Sciences, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
Pijper
Dirk
D
van Summeren
Ruben P
RP
Hoen
Rob
R
Smit
Christian
C
de Boer
Johannes W
JW
Hage
Ronald
R
Alsters
Paul L
PL
Feringa
Ben L
BL
Browne
Wesley R
WR
D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D004583:Electrons; D005650:Fumarates / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry*; D006900:Hydroxylation; D008301:Maleimides / Q000737:chemistry; D008345:Manganese / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D005650:Fumarates; D008301:Maleimides; D008345:Manganese; C035088:diethyl fumarate; D006861:Hydrogen Peroxide