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Volumn 132, Issue 32, 2010, Pages 11045-11057

Practical new silyloxy-based alkyne metathesis catalysts with optimized activity and selectivity profiles

Author keywords

[No Author keywords available]

Indexed keywords

2-BUTYNE; ACTIVE SPECIES; ALKYLIDYNES; ALKYNE METATHESIS; AMBIENT TEMPERATURES; CATALYTIC ACTIVITY; CHEMICAL YIELDS; HIGH YIELD; IN-SITU; MOLYBDENUM NITRIDE; NATURAL PRODUCTS; NEW TOOLS; PHENANTHROLINES; REACTION MIXTURE; SILANOLATES; SODIUM MOLYBDATE; SYNTHESIS ROUTE;

EID: 77955563276     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja104800w     Document Type: Article
Times cited : (232)

References (174)
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    • In addition to the established chemistry of alkynes, recent advances in the carbophilic activation of triple bonds with noble metal catalysts hold particular promise in this regard; see: Fürstner, A. and Davies, P. W. Angew. Chem., Int. Ed. 2007, 46, 3410
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    • In most cases the nature of the active catalyst in solution is unknown, even though it might be guessed on the basis of the extensive knowledge of the chemistry of metal alkylidynes. Therefore, the expressions catalyst and precatalyst are not rigorously distinguished in this publication.
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    • Complex 22 was prepared according to ref 60. A detailed procedure is described in the Supporting Information.
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    • Alkyne metathesis reactions using Mortreux-type catalyst mixtures have previously been run in the presence of MS 4 Å in order to remove traces of moisture. However, it was reported later that carefully dried solvents make the addition of MS 4 Å unnecessary. No effect of this additive on the conversion was noticed; see
    • Alkyne metathesis reactions using Mortreux-type catalyst mixtures have previously been run in the presence of MS 4 Å in order to remove traces of moisture. However, it was reported later that carefully dried solvents make the addition of MS 4 Å unnecessary. No effect of this additive on the conversion was noticed; see: Huc, V., Weihofen, R., Martin-Jimenez, I., Oulié, P., Lepetit, C., Lavigne, G., and Chauvin, R. New J. Chem. 2003, 27, 1412
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    • MS 5 Å is slightly more effective than MS 4 Å, whereas the use of MS 3 Å has little effect, if any. Since MS 3 Å, however, is an efficient trap for water, this comparison shows that the observed rate acceleration and the improved yields are not caused by ensuring a rigorously dry medium.
    • MS 5 Å is slightly more effective than MS 4 Å, whereas the use of MS 3 Å has little effect, if any. Since MS 3 Å, however, is an efficient trap for water, this comparison shows that the observed rate acceleration and the improved yields are not caused by ensuring a rigorously dry medium.
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    • As expected, powdered MS 5 Å is more effective than the use of pellets, and about 2 mg/μmol butyne turned out to be optimal.
    • As expected, powdered MS 5 Å is more effective than the use of pellets, and about 2 mg/μmol butyne turned out to be optimal.
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    • 2 as the reaction medium, did not go to complete conversion, even in the presence of molecular sieves. Reactions in THF were much slower than those in the other solvents investigated.
    • 2 as the reaction medium, did not go to complete conversion, even in the presence of molecular sieves. Reactions in THF were much slower than those in the other solvents investigated.
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    • 2O/MS 5 Å.
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    • As the reactions with complex 15 have to be performed at higher temperature, addition of molecular sieves is usually not necessary and sometimes even disadvantageous due to possible side reactions at this temperature.
    • As the reactions with complex 15 have to be performed at higher temperature, addition of molecular sieves is usually not necessary and sometimes even disadvantageous due to possible side reactions at this temperature.


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