Rajkumar Subramani, Karthik Shanmugam, Gandhi Thirumanavelan
†Materials Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632014, Tamil Nadu, India.
‡Centre for Nanomaterials, VIT University, Vellore 632014, Tamil Nadu, India.
J Org Chem. 2015 Jun 5;80(11):5532-45. doi: 10.1021/acs.joc.5b00411. Epub 2015 Apr 21.
A Ru(II)-catalyzed C-H arylation approach has been developed utilizing β-carboline alkaloids as the directing group. Selective formations of diarylated products from moderate to excellent yields were accomplished. Broad substrate scope with excellent functional group tolerance for C1-phenyl/thienyl/PAHs-β-carbolines was demonstrated. X-ray crystal structure of cycloruthenated complex 2cr and no arylation reaction with model substrate 13 strongly suggests that N2 is the directing group than N9 in C1-aryl-β-carbolines. Catalytic properties and stability of the cycloruthenated complexes have been explored. Library of biologically relevant new β-carboline derivatives and isolation of its cycloruthenated intermediates are the highlights of this work.
已开发出一种利用β-咔啉生物碱作为导向基团的钌（II）催化C-H芳基化方法。实现了从中等产率到优异产率的二芳基化产物的选择性形成。展示了对C1-苯基/噻吩基/多环芳烃-β-咔啉具有优异官能团耐受性的广泛底物范围。环钌化配合物2cr的X射线晶体结构以及与模型底物13无芳基化反应强烈表明，在C1-芳基-β-咔啉中，N2是比N9更好的导向基团。已探索了环钌化配合物的催化性能和稳定性。具有生物学相关性的新型β-咔啉衍生物文库及其环钌化中间体的分离是这项工作的亮点。
