Osmium-Catalyzed Oxidative Cyclization of Dienes and Their Derivatives

Pilgrim, Ben S.; Donohoe, Timothy J.

doi:10.1021/jo302719y

Cited by 36 publications

(17 citation statements)

References 61 publications

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“…The RuO 4 -catalyzed oxidative mono-cyclization of 1,n-dienes has previously been reviewed [72]. Recent developments in this fields, mostly concerning the OsO 4 chemistry, have been summarized in a review by Pilgrim and Donohoe [100] where a comparative picture of the oxidative cyclizations of 1,5- and 1,6-dienes, and related processes mediated by various metal oxo-species, including RuO 4 , has been presented.…”

Section: Ruthenium Tetroxide Chemistrymentioning

confidence: 99%

Ruthenium Tetroxide and Perruthenate Chemistry. Recent Advances and Related Transformations Mediated by Other Transition Metal Oxo-species

Piccialli

2014

Molecules

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Abstract:In the last years ruthenium tetroxide is increasingly being used in organic synthesis. Thanks to the fine tuning of the reaction conditions, including pH control of the medium and the use of a wider range of co-oxidants, this species has proven to be a reagent able to catalyse useful synthetic transformations which are either a valuable alternative to established methods or even, in some cases, the method of choice. Protocols for oxidation of hydrocarbons, oxidative cleavage of C-C double bonds, even stopping the process at the aldehyde stage, oxidative cleavage of terminal and internal alkynes, oxidation of alcohols to carboxylic acids, dihydroxylation of alkenes, oxidative degradation of phenyl and other heteroaromatic nuclei, oxidative cyclization of dienes, have now reached a good level of improvement and are more and more included into complex synthetic sequences. The perruthenate ion is a ruthenium (VII) oxo-species. Since its introduction in the mid-eighties, tetrapropylammonium perruthenate (TPAP) has reached a great popularity among organic chemists and it is mostly employed in catalytic amounts in conjunction with N-methylmorpholine N-oxide (NMO) for the mild oxidation of primary and secondary alcohols to carbonyl compounds. Its use in the oxidation of other functionalities is known and recently, its utility in new synthetic transformations has been demonstrated. New processes, synthetic applications, theoretical studies and unusual transformations, published in the last eight years (2006)(2007)(2008)(2009)(2010)(2011)(2012)(2013), in the chemistry of these two oxo-species, will be covered in this review with the aim of offering a clear picture of their reactivity. When appropriate, related oxidative transformations mediated by other metal oxo-species will be presented to highlight similarities and differences. An historical overview of some aspects of the ruthenium tetroxide chemistry will be presented as well.

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Section: Ruthenium Tetroxide Chemistrymentioning

confidence: 99%

Ruthenium Tetroxide and Perruthenate Chemistry. Recent Advances and Related Transformations Mediated by Other Transition Metal Oxo-species

Piccialli

2014

Molecules

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“…In this catalytic reaction, Os V O(OH) species work as the active oxidant, and just one equivalent of H 2 O 2 is enough to give cis ‐diols selectively in high yields and with high oxidant efficiency. Furthermore, it should be emphasized that our catalytic system is based on the concept that “all osmium reagents are not equally toxic as OsO 4 ”, as mentioned by Donohoe et al 12. For example, the osmium(VI) compound K 2 [OsO 2 (OH) 4 ] is not volatile and its LD 50 is reduced by more than 200‐fold (2.69 g kg −1 ) when compared with OsO 4 .…”

Section: Introductionmentioning

confidence: 99%

Osmium(III) and Osmium(V) Complexes Bearing a Macrocyclic Ligand: A Simple and Efficient Catalytic System for cis‐Dihydroxylation of Alkenes with Hydrogen Peroxide

Sugimoto

Ashikari

Itoh

2013

Chemistry An Asian Journal

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A simple protocol that uses [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1; L-N4Me2 = N,N'-dimethyl-2,11-diaza[3.3](2,6)pyridinophane) as a catalyst and H2O2 as a terminal oxidant for efficient cis-1,2-dihydroxylation of alkenes is presented. Unfunctionalized (or aliphatic) alkenes and alkenes/styrenes containing electron-withdrawing groups are selectively oxidized to the corresponding vicinal diols in good to excellent yields (46-99 %). In the catalytic reactions, the stoichiometry of alkene:H2O2 is 1:1, and thus the oxidant efficiency is very high. For the dihydroxylation of cyclohexene, the catalytic amount of 1 can be reduced to 0.01 mol % to achieve a very high turnover number of 5500. The active oxidant is identified as the Os(V)(O)(OH) species (2), which is formed via the hydroperoxide adduct, an Os(III)(OOH) species. The active oxidant 2 is successfully isolated and crystallographically characterized.

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“…111,112 Many advances in Os-mediated oxidative cyclization have been proposed and reviewed by the team of Donohoe. 113 oxidative cyclization of homoallylic alcohols is achieved by palladium, using PhI(OAc) 2 as a reoxidant (Scheme 34). 114 In this case, good enantiomeric excess is obtained thanks to a spirobis-oxazoline ligand but no indications are given regarding the major enantiomer.…”

Section: Oxidative Cyclizationsmentioning

confidence: 99%

Recent advances in the synthesis of tetrahydrofurans and applications in total synthesis

et al. 2016

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Mousseron. His research interests include the total synthesis of oxygenated cyclic and non cyclic metabolites of polyunsaturated fatty acids, mainly leukotrienes, iso-, phyto-and neuroprostanes, as well as dihydroxylated PUFAs and more recently lipophenols and the understanding of the role of such bioactive lipids and lipophenols by developing collaborations with chemists, biochemists, biologists and clinicians across the world. Jean-Marie Galano studied chemistry at Paul Cézanne Université Marseille and obtained his PhD under the supervision of Honoré Monti in 2001. He then moved to the University of Oxford to pursue a postdoctoral fellowship with David H. Hodgson on the development of new methods for the total synthesis of natural products. In October 2005 he joined the CNRS as a Chargé de Recherche at Université of Montpellier. His research focuses on the total synthesis and discovery of new lipid metabolites, and to discover their potential implications in human health. AbstractMany natural products contain tetrahydrofuran (THF) moieties. Those molecules, often biologically active, may be structurally diverse, e.g. cis or trans THF, mono-, di-, tri-or tetrasubstituted on the furan ring. Thus, the construction of THF is of great interest for the community of organic chemists; especially in developing new methodologies, and applying them in the total synthesis of natural products. The aim of this review is to report recent advances in the field of THF synthesis, as well as the application of these methods to the synthesis of bioactive compounds.

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Osmium-Catalyzed Oxidative Cyclization of Dienes and Their Derivatives

Cited by 36 publications

References 61 publications

Ruthenium Tetroxide and Perruthenate Chemistry. Recent Advances and Related Transformations Mediated by Other Transition Metal Oxo-species

Ruthenium Tetroxide and Perruthenate Chemistry. Recent Advances and Related Transformations Mediated by Other Transition Metal Oxo-species

Osmium(III) and Osmium(V) Complexes Bearing a Macrocyclic Ligand: A Simple and Efficient Catalytic System for cis‐Dihydroxylation of Alkenes with Hydrogen Peroxide

Recent advances in the synthesis of tetrahydrofurans and applications in total synthesis

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