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Volumn 29, Issue 23, 2010, Pages 6308-6320

Lanthanide- and actinide-mediated terminal alkyne hydrothiolation for the catalytic synthesis of markovnikov vinyl sulfides

Author keywords

[No Author keywords available]

Indexed keywords

1-HEXYNE; ALKYNE INSERTIONS; ALKYNYLS; AROMATIC THIOL; BENZYLIC; CATALYST CONCENTRATION; CATALYTIC SYNTHESIS; DEUTERIUM EXCHANGE; DEUTERIUM LABELING; DIFFERENT SUBSTRATES; FIRST-ORDER; HYDROTHIOLATION; KINETIC INVESTIGATIONS; LANTHANIDES; MEDIATED REACTIONS; METAL-THIOLATE; PRECATALYSTS; PROTONOLYSIS; RADICAL INHIBITOR; TERMINAL ALKYNE; TERPINENE; TRANSITION STATE;

EID: 78649849420     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om100697h     Document Type: Article
Times cited : (82)

References (174)
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    • This diminished activity is attributed to the greater RS-H bond enthalpy in alihpatic versus aromatic thiols. See ref 6m
    • This diminished activity is attributed to the greater RS-H bond enthalpy in alihpatic versus aromatic thiols. See ref 6m.
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    • See Supporting Information for bond enthalpy calculations
    • See Supporting Information for bond enthalpy calculations.
  • 114
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    • Attempts to insert unactivated olefins into Ln-SR and An-SR bonds have thus far been unsuccessful
    • Attempts to insert unactivated olefins into Ln-SR and An-SR bonds have thus far been unsuccessful.
  • 115
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    • See Supporting Information for bond enthalpy calculations
    • See Supporting Information for bond enthalpy calculations.
  • 127
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    • Similar attempts with stirring show drastically reduced conversion, possibly the result of accelerated catalyst aggregation
    • Similar attempts with stirring show drastically reduced conversion, possibly the result of accelerated catalyst aggregation.
  • 128
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    • note
    • Alkyne dimers are not observed in NMR-scale reactions. The presence of the small quantities of dimer early in the preparative scale likely results from 5 -mediated dimerization of 1-hexyne before the benzylmercaptan thaws.
  • 130
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    • Precipitate colors vary as a function of lanthanide. See Supporting Information
    • Precipitate colors vary as a function of lanthanide. See Supporting Information.
  • 133
    • 78649862168 scopus 로고    scopus 로고
    • It is unclear if this Markovnikov hydrothiolation activity is the result of the heterogeneous species exhibiting hydrothiolation activity or if it results from traces of homogeneous catalyst still remaining in solution
    • It is unclear if this Markovnikov hydrothiolation activity is the result of the heterogeneous species exhibiting hydrothiolation activity or if it results from traces of homogeneous catalyst still remaining in solution.
  • 136
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    • The turnover frequency for complex 1 was unobtainable due to heavy precipitate formation immediately after addition of excess thiol
    • The turnover frequency for complex 1 was unobtainable due to heavy precipitate formation immediately after addition of excess thiol.
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    • 6.
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    • No NMR data on ring cleavage rates for complex 4 were obtainable due to large quantities of precipitation in the NMR tube
    • No NMR data on ring cleavage rates for complex 4 were obtainable due to large quantities of precipitation in the NMR tube.
  • 139
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    • Images of the resulting precipitates are provided in the Supporting Information
    • Images of the resulting precipitates are provided in the Supporting Information.
  • 140
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    • Unfortunately, due to rapid catalyst precipitation, turnover frequencies could not be accurately measured for most thiols and alkynes, preventing quantitative comparison of substrate hydrothiolation activity
    • Unfortunately, due to rapid catalyst precipitation, turnover frequencies could not be accurately measured for most thiols and alkynes, preventing quantitative comparison of substrate hydrothiolation activity.
  • 141
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    • Additional internal alkyne and terminal α-trisubstituted alkynes were surveyed and displayed little or no activity
    • Additional internal alkyne and terminal α-trisubstituted alkynes were surveyed and displayed little or no activity.
  • 147
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    • A plot of ln(rate) vs ln([catalyst]) does not give a linear trend, furthur demonstrating that the hydrothiolation reaction is not second-order with respect to [catalyst]
    • A plot of ln(rate) vs ln([catalyst]) does not give a linear trend, furthur demonstrating that the hydrothiolation reaction is not second-order with respect to [catalyst].
  • 149
    • 78649827240 scopus 로고    scopus 로고
    • Large excesses of alkyne are found to delay precipitate formation
    • Large excesses of alkyne are found to delay precipitate formation.
  • 150
    • 78649826704 scopus 로고    scopus 로고
    • 2 is observed, it can be estimated that thiol-mediated protonolysis is >50× faster than analogous alkyne-mediated protonolysis
    • 2 is observed, it can be estimated that thiol-mediated protonolysis is >50× faster than analogous alkyne-mediated protonolysis.
  • 151
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    • tBuSH resonance (1.6 ppm)
    • tBuSH resonance (1.6 ppm).
  • 152
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    • note
    • 2An< complexes is observed occurring at approximately the same rate. Meanwhile, a comparison of Cp* ring cleavage from complexes 34 and 35 evidences ring cleavage from U at approximately 1/4 the rate observed for Th.
  • 155
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    • Rate measured as beginning of reaction before signifigant ligand protonolysis
    • Rate measured as beginning of reaction before signifigant ligand protonolysis.
  • 157
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    • Cp-based zirconium complexes are not observed to form insoluable aggregates except at extremely high thiol concentrations, exceeding 1 M, and after extended heating. Despite the observed aggregation, no ligand cleavage is observed
    • Cp-based zirconium complexes are not observed to form insoluable aggregates except at extremely high thiol concentrations, exceeding 1 M, and after extended heating. Despite the observed aggregation, no ligand cleavage is observed.
  • 165
    • 78649838792 scopus 로고    scopus 로고
    • Control experiments performed without catalyst evidence the formation of free radical-derived anti-Markonikov products under reaction conditions presented in this study
    • Control experiments performed without catalyst evidence the formation of free radical-derived anti-Markonikov products under reaction conditions presented in this study.
  • 166
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    • The radical inhibitor is added in a 1:1 molar ratio with alkyne
    • The radical inhibitor is added in a 1:1 molar ratio with alkyne.
  • 174
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    • As is discussed earlier, Markovnikov selectivity is suggestive of alkyne insertion into the M-SR bond
    • As is discussed earlier, Markovnikov selectivity is suggestive of alkyne insertion into the M-SR bond.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.