Olefin epoxidation with inorganic peroxides. Solutions to four long-standing controversies on the mechanism of oxygen transfer

Dirk V. Deubel; Gernot Frenking; Philip Gisdakis; Wolfgang A. Herrmann; Notker Rösch; Jörg Sundermeyer

doi:10.1021/ar0400140

Olefin epoxidation with inorganic peroxides. Solutions to four long-standing controversies on the mechanism of oxygen transfer

Dirk V. Deubel
, Gernot Frenking
, Philip Gisdakis
, Wolfgang A. Herrmann
, Notker Rösch
, Jörg Sundermeyer

Research output: Contribution to journal › Review article › peer-review

144 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	645-652
Number of pages	8
Journal	Accounts of Chemical Research
Volume	37
Issue number	9
DOIs	https://doi.org/10.1021/ar0400140
State	Published - Sep 2004

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@article{352306e502d844a087b997ec1e10fe43,

title = "Olefin epoxidation with inorganic peroxides. Solutions to four long-standing controversies on the mechanism of oxygen transfer",

abstract = "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.",

author = "Deubel, \{Dirk V.\} and Gernot Frenking and Philip Gisdakis and Herrmann, \{Wolfgang A.\} and Notker R{\"o}sch and J{\"o}rg Sundermeyer",

year = "2004",

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doi = "10.1021/ar0400140",

language = "English",

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journal = "Accounts of Chemical Research",

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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 - https://www.scopus.com/pages/publications/4644228277

U2 - 10.1021/ar0400140

DO - 10.1021/ar0400140

M3 - Review article

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 -

Olefin epoxidation with inorganic peroxides. Solutions to four long-standing controversies on the mechanism of oxygen transfer

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