84255-35-6Relevant articles and documents
Suzuki-Miyaura Cross-Coupling of Amides using Well-Defined, Air-Stable [(PR3)2Pd(II)X2] Precatalysts
Li, Guangchen,Ma, Siyue,Szostak, Michal,Zhou, Tongliang
supporting information, (2020/05/26)
A versatile method for the Suzuki-Miyaura cross-coupling of amides using highly active, well-defined, and air-stable Pd?phosphine precatalysts is reported. Most notably, the method represents the first example of using practical and operationally-simple Pd(II)?phosphine precatalysts in the emerging amide bond cross-coupling manifold. The reactions are efficient at 0.10 mol% loading, furnishing biaryl ketones with high chemoselectivity for N?C(O) bond cleavage. This versatile method enables for the first time to achieve Pd?phosphine-catalyzed cross-coupling of amides at ppm loading. This C?N cross-coupling can be used to efficiently furnish pharmaceutical intermediates by orthogonal Pd-catalyzed cross-couplings. We fully expect that operationally-simple [(PR3)2Pd(II)X2] precatalysts as effective triggers for N?C(O) cross-coupling will be of broad synthetic and catalytic interest. (Figure presented.).
N-Methylamino Pyrimidyl Amides (MAPA): Highly Reactive, Electronically-Activated Amides in Catalytic N-C(O) Cleavage
Meng, Guangrong,Lalancette, Roger,Szostak, Roman,Szostak, Michal
, p. 4656 - 4659 (2017/09/12)
Despite recent progress in catalytic cross-coupling technologies, the direct activation of N-alkyl-N-aryl amides has been a challenging transformation. Here, we report the first Suzuki cross-coupling of N-methylamino pyrimidyl amides (MAPA) enabled by the controlled nN → πAr conjugation and the resulting remodeling of the partial double bond character of the amide bond. The new mode of amide activation is suitable for generating acyl-metal intermediates from unactivated primary and secondary amides.
Pd-PEPPSI: A General Pd-NHC Precatalyst for Suzuki-Miyaura Cross-Coupling of Esters by C-O Cleavage
Shi, Shicheng,Lei, Peng,Szostak, Michal
, p. 3784 - 3789 (2017/10/13)
The Suzuki-Miyaura cross-coupling of aryl esters by selective C-O bond cleavage represents a powerful methodology in organic synthesis. Here, we report that versatile, easily prepared, well-defined Pd-PEPPSI type precatalysts serve as highly reactive catalysts for the direct Suzuki-Miyaura cross-coupling of esters. Sterically and electronically diverse aryl esters couple with arylboronic acids in good to excellent yields using a single, operationally simple protocol. Kinetic studies demonstrate that the cross-coupling of aryl esters proceeds with rates similar to the cross-coupling of amides. This study strongly supports the use of well-defined Pd(II)-NHC precatalysts bearing pyridine throw-away ligands for the selective C(acyl) cleavage of bench-stable carboxylic acid derivatives. Considering the modular scaffold of Pd-NHC precatalysts, we envision that the method will be of general interest for the development of new catalysts for C-O cleavage reactions.