Cross-Coupling Reactions of Alkenylsilanolates. Investigation of the Mechanism and Identification of Key Intermediates through Kinetic Analysis

Journal of the American Chemical Society

Volumn 126, Issue 15, 2004, Pages 4876-4882

  Denmark, Scott E ^a   Sweis, Ramzi F ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; COMPLEXATION; CONCENTRATION (PROCESS); FLUORINE COMPOUNDS; PALLADIUM; POTASSIUM COMPOUNDS; REACTION KINETICS;

2-IODOTHIOPHENE; CROSS-COUPLING REACTIONS; KINETIC ANALYSIS;

SILICON COMPOUNDS;

2 IODOTHIOPHENE; ALCOHOL DERIVATIVE; ALKENYL GROUP; FLUORIDE; IODIDE; IODINE DERIVATIVE; OXYGEN; PALLADIUM; PALLADIUM COMPLEX; POTASSIUM DERIVATIVE; POTASSIUM HEPTENYLDIMETHYLSILANOLATE; SILANE DERIVATIVE; SILICON; THIOPHENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION KINETICS; CONCENTRATION (PARAMETERS); CROSS COUPLING REACTION; CROSS LINKING; METAL BINDING; OXIDATION; REACTION ANALYSIS;

ALKENES; KINETICS; PALLADIUM; SILANES; THIOPHENES;

EID: 1842862941     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0372356     Document Type: Article

References (35)

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25. At this point, we cannot rigorously rule out the possibility that transmetalation does not involve the formation of a diorganopalladium(II) species as is assumed for cross-coupling in general. If so, a different late-appearing step that depends on silanolate may be turnover-limiting.
26. (a) Disiloxane was not formed under these conditions. If this were not the case, calculation of the silanolate concentration would be determined from the amounts of both silanol and disiloxane formed.
27. (b) This check was necessary due to the slow deterioration of silanolate in the stock solution over several weeks.
28. Details of the procedure and analysis are provided in the Supporting Information.
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30. The lack of solubility of KI in this reaction mixture suggested that formation of i cannot be reversible.
31. -1, ΔH = 8.94 kcal/mol, ΔS = -6.12 eu, and ΔG = 10.74 kcal/mol.
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35. The kinetic equation cannot rigorously exclude the possibility that silanolate activation is necessary for the breakdown of an intermediate after the turnover-limiting step. This would be a kinetically silent event and becomes reasonable if the mechanism of transmetalation is different from the current view.