Issue 32, 2023

Aryl C–H bond functionalization with diphenyldiazomethane induced by rare-earth metal alkyl complexes

Abstract

The first examples of regioselective aryl ortho-C–H functionalization with diphenyldiazomethane for the construction of Caryl–Nhydrazinato bonds were accomplished via the activation of C–H bonds and the subsequent reaction of diphenyldiazomethane with the RE–Caryl bond. The reactions of rare-earth metal monoalkyl complexes LRE(CH2SiMe3)(THF)2 (L = 2,5-[(2-pyrrolyl)CPh2]2(N-Me-pyrrole)) supported by a neutral N-methylpyrrole anchored dipyrrolyl ligand with 2 equiv. of Ph2CN2 gave irreversibly unprecedented hydrazonato-functionalized imino rare-earth metal complexes LRE(Ph2C[double bond, length as m-dash]NNC6H4-(o-C[double bond, length as m-dash]NHPh) (RE = Y (2a), Lu (2a′)) in good yields involving a rather complex process including the interaction of a diazo unit with a RE–Calkyl bond, a β-H elimination, a N–N cleavage, 1,4-hydrogen transfer and the subsequent C–N coupling with another diphenyldiazomethane. More important is that regioselective aryl C–H bond functionalization with diphenyldiazomethane to construct the Caryl–Nhydrazinato bonds can be easily achieved by three-component reactions of rare-earth metal monoalkyl complexes, a wide range of substituted imines (including aldimines, ketimines or analogous 2-phenylpyridine) and diphenyldiazomethane, affording various hydrazonato-functionalized phenyl, thienyl imino or pyridyl rare-earth metal complexes 2b–2j at room temperature. A further study indicated that the substituents on the phenyl ring have a great effect on the reaction pathway and governed the Caryl–Nhydrazinato bond construction. Moreover, the experimental studies show that the formation of the Caryl–Nhydrazinato bonds is thermodynamically facile, which could be realized at room temperature easily.

Graphical abstract: Aryl C–H bond functionalization with diphenyldiazomethane induced by rare-earth metal alkyl complexes

Supplementary files

Article information

Article type
Paper
Submitted
04 Jun 2023
Accepted
19 Jul 2023
First published
31 Jul 2023

Dalton Trans., 2023,52, 11315-11324

Aryl C–H bond functionalization with diphenyldiazomethane induced by rare-earth metal alkyl complexes

D. Guo, T. Rajeshkumar, S. Zhu, Q. Yuan, D. Hong, S. Zhou, X. Zhu, L. Maron and S. Wang, Dalton Trans., 2023, 52, 11315 DOI: 10.1039/D3DT01714A

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