School of Chemistry, The University of Sydney, Sydney, N.S.W., Australia.
Chemistry. 2013 Jan 28;19(5):1672-6. doi: 10.1002/chem.201203159. Epub 2012 Dec 18.
Facile strategies were developed for the versatile functionalization of platinum(IV) axial sites, allowing for easy accessibility to unsymmetric mono- and mixed-carboxylato, as well as symmetric di-substituted platinum(IV) complexes. The first method involves the direct oxidation and carboxylation of the platinum(II) center using an appropriate peroxide and the carboxylate of choice to firstly yield a monocarboxylato monohydroxido platinum(IV) complex. This platinum(IV) intermediate can undergo further carboxylation to give rise to a mixed-carboxylato platinum(IV) complex. The second method involves the activation of the carboxylate of choice by a common carbodiimide coupling reagent, and its reaction with a dihydroxido platinum(IV) precursor to give the monocarboxylato platinum(IV) complex. Uronium salts can be employed to promote efficient dicarboxylation of the dihydroxido platinum(IV) precursor. Lastly, an axial azide pendant group was demonstrated to be suitable for orthogonal "click" conjugation reactions.
开发了简便的策略来实现铂(IV)轴向位置的多功能官能化，使不对称的单羧基和混合羧基以及对称的二取代铂(IV)配合物易于获得。第一种方法涉及使用适当的过氧化物和所需的羧酸盐直接氧化和羧化铂(II)中心，首先生成单羧基单羟基金属(IV)配合物。该铂(IV)中间体可以进一步进行羧化反应，生成混合羧基铂(IV)配合物。第二种方法涉及通过常见的碳二亚胺偶联试剂活化所需的羧酸盐，然后使其与二羟基金属(IV)前体反应，得到单羧基铂(IV)配合物。可以使用尿嘧啶盐来促进二羟基金属(IV)前体的高效二羧化反应。最后，展示了轴向叠氮基团适合正交“点击”共轭反应。
