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Dihydroxylation of alkenes using a Tp–osmium complex

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Title: Dihydroxylation of alkenes using a Tp–osmium complex
Authors: Dehestani, Ahmad1, Wu, Adam1, Hayoun, Rebecca1, Kaminsky, Werner, Mayer, James M. mayer@chem.washington.edu
Source: Inorganica Chimica Acta. Sep2009, Vol. 362 Issue 12, p4534-4538. 5p.
Subjects: Hydroxylation, Alkenes, Metal complexes, Organoosmium compounds, Temperature effect, Benzoic acid, Stilbene, Molecular structure
Abstract: Abstract: The reaction of TpOsVI(N)(OH)2 (1) [Tp=hydrotris(1-pyrazolyl)borate], m-chloroperbenzoic acid (m-CPBA), and trans-stilbene in C6H6 at room temperature gives the diolate complex TpOsVI(N)(trans-O2C2H2Ph2) (2) and m-chlorobenzoic acid (m-CBA). The trans configuration of the stilbene is retained in the diolate complex as shown in the crystal structure of 2. Complex 2 is hydrolyzed by 2 equivalents of aqueous HCl in CD2Cl2 to give rac-hydrobenzoin, the product of cis-dihydroxylation, and TpOsVI(N)Cl2. cis-Stilbene, styrene, cyclohexene, trans-dimethyl fumarate, trans-methyl cinnamate, and trans-4-dimethylamino-4′-nitrostilbene are also converted to their corresponding free diol products by reaction with 1 and m-CPBA in CD2Cl2, and then aqueous HCl. In aqueous HBF4, oxidation of the water-soluble olefin, 4-styrenesulfonic acid, by 1 is modestly catalytic (15 turnovers in 3h) with excess PbO2 as the oxidant. Under non-acidic conditions, the diolate complexes are inert and catalysis is precluded. Mechanistic experiments implicate an oxidizing osmium complex as an intermediate in these reactions. [Copyright &y& Elsevier]
Copyright of Inorganica Chimica Acta is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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Header DbId: egs
DbLabel: Engineering Source
An: 43874323
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
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  Data: Dihydroxylation of alkenes using a Tp–osmium complex
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  Data: <searchLink fieldCode="AR" term="%22Dehestani%2C+Ahmad%22">Dehestani, Ahmad</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Wu%2C+Adam%22">Wu, Adam</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Hayoun%2C+Rebecca%22">Hayoun, Rebecca</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Kaminsky%2C+Werner%22">Kaminsky, Werner</searchLink><br /><searchLink fieldCode="AR" term="%22Mayer%2C+James+M%2E%22">Mayer, James M.</searchLink><i> mayer@chem.washington.edu</i>
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  Data: <searchLink fieldCode="DE" term="%22Hydroxylation%22">Hydroxylation</searchLink><br /><searchLink fieldCode="DE" term="%22Alkenes%22">Alkenes</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+complexes%22">Metal complexes</searchLink><br /><searchLink fieldCode="DE" term="%22Organoosmium+compounds%22">Organoosmium compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Temperature+effect%22">Temperature effect</searchLink><br /><searchLink fieldCode="DE" term="%22Benzoic+acid%22">Benzoic acid</searchLink><br /><searchLink fieldCode="DE" term="%22Stilbene%22">Stilbene</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink>
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  Data: Abstract: The reaction of TpOsVI(N)(OH)2 (1) [Tp=hydrotris(1-pyrazolyl)borate], m-chloroperbenzoic acid (m-CPBA), and trans-stilbene in C6H6 at room temperature gives the diolate complex TpOsVI(N)(trans-O2C2H2Ph2) (2) and m-chlorobenzoic acid (m-CBA). The trans configuration of the stilbene is retained in the diolate complex as shown in the crystal structure of 2. Complex 2 is hydrolyzed by 2 equivalents of aqueous HCl in CD2Cl2 to give rac-hydrobenzoin, the product of cis-dihydroxylation, and TpOsVI(N)Cl2. cis-Stilbene, styrene, cyclohexene, trans-dimethyl fumarate, trans-methyl cinnamate, and trans-4-dimethylamino-4′-nitrostilbene are also converted to their corresponding free diol products by reaction with 1 and m-CPBA in CD2Cl2, and then aqueous HCl. In aqueous HBF4, oxidation of the water-soluble olefin, 4-styrenesulfonic acid, by 1 is modestly catalytic (15 turnovers in 3h) with excess PbO2 as the oxidant. Under non-acidic conditions, the diolate complexes are inert and catalysis is precluded. Mechanistic experiments implicate an oxidizing osmium complex as an intermediate in these reactions. [Copyright &y& Elsevier]
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  Group: Ab
  Data: <i>Copyright of Inorganica Chimica Acta is the property of Elsevier B.V. and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1016/j.ica.2009.05.004
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        Text: English
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        StartPage: 4534
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      – SubjectFull: Hydroxylation
        Type: general
      – SubjectFull: Alkenes
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      – SubjectFull: Metal complexes
        Type: general
      – SubjectFull: Organoosmium compounds
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      – SubjectFull: Temperature effect
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      – SubjectFull: Benzoic acid
        Type: general
      – SubjectFull: Stilbene
        Type: general
      – SubjectFull: Molecular structure
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      – TitleFull: Dihydroxylation of alkenes using a Tp–osmium complex
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              Text: Sep2009
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