Rationale behind the resistance of dialkylbiaryl phosphines toward oxidation by molecular oxygen
Rationale behind the resistance of dialkylbiaryl phosphines toward oxidation by molecular oxygen
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DOI：
10.1021/ja0683180
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发表时间：
2007-04-25
影响因子：
15
通讯作者：
Buchwald, Stephen L.
中科院分区：
文献类型：
--
作者：
Barder, Timothy E.;Buchwald, Stephen L.
富含电子的二烷基联芳基膦是一类常见的钯催化交叉偶联反应的支撑配体，对分子氧的氧化具有很高的抵抗力。这里提出了这类膦配体表现这一性质的可能原因。实验和理论数据表明，磷中心和联芳基主链的2‘和6’位上的两个烷基取代基在抑制这类配体的氧化中起着重要作用。
Electron-rich dialkylbiaryl phosphines, which comprise a common class of supporting ligands for Pd-catalyzed cross-coupling reactions, are highly resistant toward oxidation by molecular oxygen. Presented herein are possible reasons why this class of phosphine ligands manifests this property. Experimental and theoretical data suggest that the two alkyl substituents on the phosphorus center and the 2' and 6' positions of the biaryl backbone play an important role in inhibiting oxidation of this class of ligands.