Promoting Difficult Carbon-Carbon Couplings: Which Ligand Does Best?

A Pd complex, cis‐[Pd(C6F5)2(THF)2] (1), is proposed as a useful touchstone for direct and simple experimental measurement of the relative ability of ancillary ligands to induce C−C coupling. Interestingly, 1 is also a good alternative to other precatalysts used to produce Pd0L. Complex 1 ranks the...

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Bibliographic Details
Published in:Angewandte Chemie 2016-10, Vol.128 (42), p.13470-13474
Main Authors: Gioria, Estefanía, del Pozo, Juan, Martínez-Ilarduya, Jesús M., Espinet, Pablo
Format: Article
Language:English
Subjects:
Carbon-carbon composites
Chemistry
Couplings
Efficiency
Homogene Katalyse
Hydrolysis
Kreuzkupplungsmechanismen
Ligands
Measuring instruments
Meters
Palladiumkatalyse
Phosphine
Reduktive Eliminierung
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Summary:A Pd complex, cis‐[Pd(C6F5)2(THF)2] (1), is proposed as a useful touchstone for direct and simple experimental measurement of the relative ability of ancillary ligands to induce C−C coupling. Interestingly, 1 is also a good alternative to other precatalysts used to produce Pd0L. Complex 1 ranks the coupling ability of some popular ligands in the order PtBu3>o‐TolPEWO‐F≈tBuXPhos>P(C6F5)3≈PhPEWO‐F>P(o‐Tol)3≈THF≈tBuBrettPhos≫Xantphos≈PhPEWO‐H≫PPh3 according to their initial coupling rates, whereas their efficiency, depending on competitive hydrolysis, is ranked tBuXPhos≈PtBu3≈o‐TolPEWO‐F>PhPEWO‐F>P(C6F5)3≫tBuBrettPhos>THF≈P(o‐Tol)3>Xantphos>PhPEWO‐H≫PPh3. This “meter” also detects some other possible virtues or complications of ligands such as tBuXPhos or tBuBrettPhos. Ausgequetscht: Der Komplex cis‐[Pd(C6F5)2(THF)2] wurde als „Zähler” genutzt, um den Effekt von Liganden auf die reduktive Eliminierung in einer C‐C‐Bindungsbildung direkt zu quantifizieren. Die Liganden konnten klassifiziert und mit anderen verglichen werden. Der Komplex ist ein guter Präkatalysator für die katalytische Palladium(0)‐Spezies PdLn.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201607089