TY - JOUR
T1 - Olefin epoxidation with inorganic peroxides. Solutions to four long-standing controversies on the mechanism of oxygen transfer
AU - Deubel, Dirk V.
AU - Frenking, Gernot
AU - Gisdakis, Philip
AU - Herrmann, Wolfgang A.
AU - Rösch, Notker
AU - Sundermeyer, Jörg
PY - 2004/9
Y1 - 2004/9
N2 - Four controversies on the mechanism of the olefin epoxidation with Mimoun-type complexes, [MoO(O2)2(OPR3)], Herrmann-type complexes, [ReO(O2)2Me], and related inorganic peroxides have inspired industrial and academic researchers in the last three decades. First, is the oxygen transfer from the peroxo complex to the olefin concerted or stepwise? Second, does the oxidant act as an electrophile or a nucleophile? Third, is the mechanism of the stoichiometric reaction also valid for catalytic protocols? Fourth, how can stereochemical information be transferred between oxidant and substrate? In this Account, we discuss answers to the long-standing questions, focusing on recent contributions from quantum chemical calculations.
AB - Four controversies on the mechanism of the olefin epoxidation with Mimoun-type complexes, [MoO(O2)2(OPR3)], Herrmann-type complexes, [ReO(O2)2Me], and related inorganic peroxides have inspired industrial and academic researchers in the last three decades. First, is the oxygen transfer from the peroxo complex to the olefin concerted or stepwise? Second, does the oxidant act as an electrophile or a nucleophile? Third, is the mechanism of the stoichiometric reaction also valid for catalytic protocols? Fourth, how can stereochemical information be transferred between oxidant and substrate? In this Account, we discuss answers to the long-standing questions, focusing on recent contributions from quantum chemical calculations.
UR - http://www.scopus.com/inward/record.url?scp=4644228277&partnerID=8YFLogxK
U2 - 10.1021/ar0400140
DO - 10.1021/ar0400140
M3 - 文献综述
AN - SCOPUS:4644228277
SN - 0001-4842
VL - 37
SP - 645
EP - 652
JO - Accounts of Chemical Research
JF - Accounts of Chemical Research
IS - 9
ER -