Pd(II)/bipyridine catalyzed conjugate addition of arylboronic acids to α,β-unsaturated amides

A new MOF-supported heterogeneous palladium catalyst Pd/NBB-1 has been synthesized successfully through the effective metal metathesis between Pd(CF 3 COO) 2 and NBB-1. NBB-1 is a two-dimensional zinc metal-organic framework constructed from 2-aminoterephthalate (NH 2 À H 2 BDC) and 2,2'-bipyridine-5-carboxylate (HBPC) by solvothermal method. The replacement efficiency of Pd(II) to Zn(II) is up to 72% after only 24 hours, which is beneficial to the catalytic application. Pd/NBB-1 with a low loading of 2 mol% works efficiently in the 1,4-addition reaction of arylboronic acids with α,β-unsaturated ketones in air, and its catalytic activity keeps unchanged after 3 reaction cycles. This work provides a new strategy to effectively prepare supported noble metal/ MOF catalysts, which would further increase the practical applications of metal-organic frameworks.

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Switchable C−H Alkylation of Aromatic Acids with Maleimides in Water: Carboxyl as a Diverse Directing Group

Liu

Zhang

et al. 2019

ChemCatChem

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A ruthenium‐catalyzed protocol to access conjugate addition or decarboxylative conjugate addition of aromatic acids with maleimides has been developed. The reaction shows interesting chemoselectivity with different substituted benzoic acids. The reaction pathway of C−H alkylation is controlled by the intrinsic property of aromatic acids but not reaction conditions. Under almost the same reaction conditions, carboxyl can act as either a classical directing group or a traceless directing group, thereby generating two kinds of products, i. e., 2‐alkyl substituted benzoic acids and alkyl substituted benzenes. These two reactions proceeded under mild and redox‐neutral conditions in neat water under the atmosphere of air, and could be easily scaled up to grams. The decarboxylative conjugate addition, where carboxyl acts as a traceless directing group, can be realized without the addition of any ligand, silver or copper salt.

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Pd(II)/bipyridine catalyzed conjugate addition of arylboronic acids to α,β-unsaturated amides

Cited by 11 publications

References 33 publications

Addition Reactions

Addition Reactions

Construction of a MOF‐Supported Palladium Catalyst via Metal Metathesis

Switchable C−H Alkylation of Aromatic Acids with Maleimides in Water: Carboxyl as a Diverse Directing Group

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