第九族金属卟啉实现的选择性碳-碳键活化的研究

Research progress on selective C-C bond activation by group 9 metalloporphyrins

过渡金属配合物实现有机物碳-碳键活化一直是有机化学领域的研究热点.活化反应中生成的金属-碳键中间体,可进一步催化转化合成新的官能化有机物.本文总结了本课题组及其他团队对第九族金属卟啉实现的选择性碳-碳键活化的研究发展,主要介绍了第九族金属卟啉活性中间体M^(Ⅰ)(por)^(−)、M^(Ⅱ)(por)自由基以及M^(Ⅲ)(por)OH(M=Ir、Rh、Co,por=卟啉二价阴离子)实现酮类、酯类、酰胺类、腈类、2,2,6,6-四甲基哌啶氮-氧-化物(TEMPO)、醚类和环烷烃等有机物的选择性碳-碳键活化当量反应,以及使用H_(2)O、异丙醇、N,N-二甲基甲酰胺(DMF)作为氢源实现碳-碳键氢解和H_(2)O作为氧化剂实现碳-碳键氧化的催化转化,并探讨了现有研究的改善以及未来发展的展望.

The selective C-C bond activation of organic molecules with transition metal complexes has been studied in great demand in organic chemistry.Transition metal-carbon bonded intermediates,generated in C-C bond activation,could be further converted to new functionalized organic compounds.This review summarizes the research progress on selective C-C bond activation by group 9 metalloporphyrins in our group and other teams.It focuses on the active M(por)intermediates,M^(Ⅰ)(por)^(-)anion,M^(Ⅱ)(por)radical and M^(Ⅲ)(por)OH(M=Ir,Rh,Co;por=porphyrinato dianion),which achieved the selective stoichiometric C-C bond activation of ketones,esters,amides,nitriles,TEMPO((2,2,6,6-tetramethylpiperidin-1-yl)oxyl),ethers and cycloalkanes,as well as the catalytic conversion for hydrogenolysis of C-C bond with H_(2)O,isopropanol,DMF as hydrogen atom source,and oxidation of C-C bond with H_(2)O as oxidant.The improvement and future development are also discussed.