Rh(II)-Catalyzed Reactions of Differentially Substituted <i>Bis</i>(diazo) Functionalities

The chemoselective reaction of donor/acceptor (D/A) and acceptor/acceptor (A/A) diazo moieties in the same molecule was examined using 3-diazo-1-(ethyl 2-diazomalonyl)indolin-2-one under rhodium(II) catalysis. The D/A diazo group undergoes selective cyclopropanation as well as XH-insertion, leaving behind the second diazo group for a further intramolecular dipolar cycloaddition reaction.本研究以3-重氮-1-(2-重氮丙二酸乙酯基)吲哚啉-2-酮为底物，在铑(II)催化体系下，探究了同一分子内给体/受体（donor/acceptor，D/A）与受体/受体（acceptor/acceptor，A/A）两种重氮基团的化学选择性反应。其中，D/A型重氮基团可选择性发生环丙烷化反应及X-H插入反应，剩余的另一类重氮基团可进一步参与分子内偶极环加成反应。