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Computational Studies on Osmium-Catalyzed Olefin Oxidation Reactions

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Computational Organometallic Chemistry

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Abstract

The oxidative functionalization of olefins is an important reaction for organic synthesis as well as for the industrial production of bulk chemicals. Various processes have been explored, among them also metal-catalyzed methods using strong oxidants like osmium tetroxide. Especially, the asymmetric dihydroxylation of olefins by osmium(VIII) complexes has proven to be a valuable reaction for the synthetic chemist. A large number of experimental studies had been conducted, but the mechanisms of the various osmium-catalyzed reactions remained a controversial issue. This changed when density functional theory calculations became available and computational studies helped to unravel the open mechanistic questions. This mini review will focus on recent mechanistic studies on osmium-mediated oxidation reactions of alkenes.

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Notes

  1. 1.

    Dihydroxylation transition states with coordinated nitrogen ligand are more favorable with syn-position of NH3 regarding the imido group, whereas the aminohydroxylation transition states proceed with anti-position. Therefore the Gibbs free reaction energies given in Table 5, column 4, do not apply for a dihydroxylation pathway with NH3-coordination.

Abbreviations

AH:

Aminohydroxylation

B3LYP:

Becke’s three-parameter hybrid functional

CLB:

para-Chlorobenzoyl-

DFT:

Density functional theory

DH:

Dihydroxylation

DHQ:

Dihydroquinine

EHT:

Extended Hueckel theory

HF:

Hartree–Fock

KIE:

Kinetic isotope effect

MEQ:

9-O-(4′-methyl-2′-quinolyl)-

NM:

N-Methylmorpholine

NMO:

N-Methylmorpholine-N-oxide

PES:

Potential energy surface

PHAL:

Phthalazine

PHN:

9-O-(9′-phenanthryl)-

pTol:

para-Tolyl-

Q2MM:

Quantum mechanical guided molecular mechanics

QCISD(T):

Quadratic configuration interaction

QM:

Quantum mechanics

QM/MM:

Quantum mechanics/molecular mechanics

tert-Bu:

tert-Butyl-

THF:

Tetrahydrofuran

TON:

Turnover number

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  1. Technische Universität Dresden, Physikalische Organische Chemie, Bergstrasse 66, 01069, Dresden, Germany

    Dominik Munz, Alexander Poethig & Thomas Strassner

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  1. Dominik Munz
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  2. Alexander Poethig
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Correspondence to Thomas Strassner .

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  1. , Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, 46556-5670, Indiana, USA

    Olaf Wiest

  2. Shenzhen Graduate School, Key Lab of Chemical Genomics, Peking University, Peking, 518055, China, People's Republic

    Yundong Wu

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Munz, D., Poethig, A., Strassner, T. (2012). Computational Studies on Osmium-Catalyzed Olefin Oxidation Reactions. In: Wiest, O., Wu, Y. (eds) Computational Organometallic Chemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-25258-7_6

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