DEVELOPMENT OF HIGHLY CHEMOSELECTIVE DEPROTONATION USING ZINCATES

锌酸盐是一种新型的化学选择性去质子剂。用LTMP和二叔丁基锌制备该剂很容易。该试剂是稳定的络合物，可用于功能化芳香化合物与亲电基团的选择性金属化。各种亲电试剂与该去质子化制备的芳基锌酸盐反应，并公开了该方法的范围和局限性。该反应成功地应用于吡啶类、异喹啉类、喹啉类等杂芳烃类化合物的脱质子反应。在取代吡啶的金属化上，观察到独特的区域选择性，当2-卤代吡啶作为底物时，a-金属化占主导地位。目前正在对这种区域选择性的根源进行进一步调查。研究了脱质子化反应在固相合成中的应用，并探讨了进一步优化反应条件的可能性。与去质子化相关的是，在聚合物载体上发现了选择性去质子化的另一种选择，并对其范围和局限性进行了研究。

As a new chemoselective deprotonative agent, TMP-zincate was designed. The agent was found to be easily prepared using LTMP and di-tert-butylzinc. The agent is stable ate complex and can be used for the selective metalation of functionalized aromatic compounds with electrophilic groups. Various electrophiles were reacted with the arylzincates prepared by this deprotonation, and the scope and limitation of the methodology was disclosed. The reaction was successfully applied for the deprotonation of heteroaromatic compounds such as pyridines, isoquinolines, quinolines, and other nitrogen heteroaromatics. On the metalation of substituted pyridines, unique regioselectivity was observed and a-metalation predominates when 2-halopyridines were employed for substrates. Further investigations on the origin of this regioselectivity are underway. Application of the deprotonation for solid phase synthesis was also investigated, and the possibility was examined although further optimization of reaction conditions are necessary. Relating the deprotonation, mesityllithium was found to be an another option for selective deprotonation on polymer support, and the investigation for the scope and limitation are underway.