Banerjee Moloy, Emond Susanna J, Lindeman Sergey V, Rathore Rajendra
Department of Chemistry, Marquette University, P.O. Box 1881, Milwaukee, Wisconsin 53201-1881, USA.
J Org Chem. 2007 Oct 12;72(21):8054-61. doi: 10.1021/jo701474y. Epub 2007 Sep 20.
We have demonstrated that reactions of diphenylmethyllithium with a variety of substituted benzophenones produces corresponding tertiary alcohols that are easily dehydrated, without any need for purification, to produce various unsymmetrical and symmetrical tetraarylethylenes in excellent yields. The simplicity of the method allows for the preparation of a variety of ethylenic derivatives in multigram (10-50 g) quantities with great ease. The methodology was successfully employed for the preparation of various triphenylethylene (TPE)-based triads (i.e., TPE-spacer-TPE) containing polyphenylene and fluoranyl-based spacers. The ready availability of various substituted tetraarylethylenes allowed us to shed light on the effect of substituents on the oxidation potentials (Eox) of various tetraarylethylenes. Moreover, the electronic coupling among the triphenylethylene moieties in various TPE-spacer-TPE triads was briefly probed by electrochemical and optical methods.
我们已经证明，二苯基甲基锂与多种取代二苯甲酮反应生成相应的叔醇，这些叔醇易于脱水，无需纯化，即可高产率地生成各种不对称和对称的四芳基乙烯。该方法的简便性使得能够轻松制备多克（10 - 50克）量的各种烯类衍生物。该方法成功用于制备包含聚亚苯基和芴基间隔基的各种基于三苯基乙烯（TPE）的三联体（即TPE - 间隔基 - TPE）。各种取代的四芳基乙烯的 readily availability 使我们能够阐明取代基对各种四芳基乙烯氧化电位（Eox）的影响。此外，通过电化学和光学方法简要探究了各种TPE - 间隔基 - TPE三联体中三苯基乙烯部分之间的电子耦合。
