Triphenylcyclopentadienyl Rhodium Complexes in Catalytic C–H Annulations. Application for Synthesis of Natural Isocoumarins
作者:Vladimir B. Kharitonov、Dmitry V. Muratov、Yulia V. Nelyubina、Ilya A. Shutkov、Alexey A. Nazarov、Dmitry A. Loginov
DOI:10.1021/acs.joc.2c02526
日期:2023.3.3
Efficient protocols for the synthesis of triphenylcyclopentadienyl rhodium halides [(1,2,4-C5Ph3H2)RhX2]2 (1a,b: X = Cl, I) starting from 1,2,4-triphenylcyclopentadiene or the cyclooctadiene derivative (1,2,4-C5Ph3H2)Rh(cod) (2) were developed. Iodide abstraction from 1b with thallium or silver salts allowed us to prepare rhodocenium [(1,2,4-C5Ph3H2)RhCp]PF6 (3PF6) and mesitylene complex [(1,2,4-C
从1,2,4-三苯基环戊二烯或_ _ _ _ _ _ _ _开发了环辛二烯衍生物(1,2,4-C 5 Ph 3 H 2 )Rh(cod) ( 2 )。用铊或银盐从1b中提取碘化物使我们能够制备铑 [(1,2,4-C 5 Ph 3 H 2 )RhCp]PF 6 ( 3 PF 6)和均三甲苯络合物[(1,2,4-C 5 Ph 3 H 2 )Rh(均三甲苯)](SbF 6 ) 2 ( 4 (SbF 6 ) 2 )。卤化物1a和b (在 0.5 mol % 负载下)通过 C(sp 2 )-H 活化方法在 C-C、C-O 和 C-N 键的构建中表现出高催化活性。它们的效率在 40 多种多环有机化合物(例如异香豆素和萘,以及异喹啉和二苯并 [ a , f]喹啉鎓盐)。开发的协议容忍范围广泛的功能组。特别是,它们成功地用于原子和步骤经济地合成羟基取代的异香豆素,包括天然产物 oospalactone 7fe。6-或