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ÇóÏÂÃæ¼¸¾ä»° µÄ·Ò룬ÊÇj.o.c.ÎÄÏ× Furthermore, the reactions of unsymmetrical para-substituted azobenzenes 1p and 1q containing electron-rich and electron-deficient groups (Me and CF3) with 2a were screened under standard reaction conditions (Scheme 1). In the case of 1p, no significant distinction of product distribution between 3pa and 3pb was observed. Moreover, this transformation is not limited to aryl isocyanates. Aliphatic isocyanates such as benzyl isocyanate (4p) and cyclopentyl isocyanate (4q) and n-hexyl isocyanate (4r) also participated in redox-neutral amidation reactions to furnish 5p−5r, respectively. At this stage, we are unclear about the formation of a mixture of E and Z isomers in the case of aryl and alkyl isocyanates In conclusion, we disclosed the rhodium(III)-catalyzed direct C−H N-sulfonyl amidation of azobenzenes with arylsulfonyl isocyanates. This protocol allows the generation of Nacylsulfonamides, which are known to be crucial synthetic precursors of biologically active compounds. In addition, this protocol was successfully applied to aryl and alkyl isocyanates to deliver ortho-amidated azobenzenes. Further applications of our protocol to the synthesis of bioactive molecules and a detailed mechanistic investigation are in progress. |
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