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Keywords = Buchwald precatalysts

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23 pages, 4715 KB  
Article
Third Generation Buchwald Precatalysts with XPhos and RuPhos: Multigram Scale Synthesis, Solvent-Dependent Isomerization of XPhos Pd G3 and Quality Control by 1H- and 31P-NMR Spectroscopy
by Svitlana O. Sotnik, Artem M. Mishchenko, Eduard B. Rusanov, Andriy V. Kozytskiy, Konstantin S. Gavrilenko, Sergey V. Ryabukhin, Dmitriy M. Volochnyuk and Sergey V. Kolotilov
Molecules 2021, 26(12), 3507; https://doi.org/10.3390/molecules26123507 - 9 Jun 2021
Cited by 8 | Viewed by 9421
Abstract
The third generation Buchwald precatalysts Pd(ABP)(Phos)(OMs) (also known as Phos Pd G3)) with XPhos and RuPhos were prepared in multigram scale by a modified procedure (ABP = fragment of C-deprotonated 2-aminobiphenyl, XPhos = 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl, RuPhos = 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl, OMs = CH3SO [...] Read more.
The third generation Buchwald precatalysts Pd(ABP)(Phos)(OMs) (also known as Phos Pd G3)) with XPhos and RuPhos were prepared in multigram scale by a modified procedure (ABP = fragment of C-deprotonated 2-aminobiphenyl, XPhos = 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl, RuPhos = 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl, OMs = CH3SO3). The 1H- and 31P-NMR spectra of the title complexes and some impurities, measured by various 1D and 2D techniques, were analyzed in detail. The solvent-dependent isomerization of Pd(ABP)(XPhos)(OMs) was studied by NMR, and the X-ray structures of two isomers were determined. The impurities in precatalysts, such as Pd(ABP)(HABP)(OMs) (HABP—neutral 2-aminobiphenyl coordinated to Pd2+ in N-monodentate mode) and PdCl2(XPhos)2, were identified and characterized by single crystal X-ray diffraction. A simple method for the quick quality control (QC) of the precatalysts, suitable for routine use, was proposed. The method was based on the assessment of the impurity content on the basis of the 1H-NMR spectra analysis. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
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14 pages, 1354 KB  
Communication
Convergent Synthesis of N,S-bis Glycosylquinolin-2-ones via a Pd-G3-XantPhos Precatalyst Catalysis
by Wafa Redjdal, Nada Ibrahim, Belkacem Benmerad, Mouad Alami and Samir Messaoudi
Molecules 2018, 23(3), 519; https://doi.org/10.3390/molecules23030519 - 26 Feb 2018
Cited by 10 | Viewed by 6120
Abstract
Buchwald-Hartwig-Migita cross-coupling of 1-thiosugars with α- or β-3-iodo-N-glycosylquinolin-2-ones has been accomplished under mild and operationally simple reaction conditions through the use of a Pd-G3 XantPhos palladacycle precatalyst. This new methodology has been successfully applied to a variety of α- or β-mono-, [...] Read more.
Buchwald-Hartwig-Migita cross-coupling of 1-thiosugars with α- or β-3-iodo-N-glycosylquinolin-2-ones has been accomplished under mild and operationally simple reaction conditions through the use of a Pd-G3 XantPhos palladacycle precatalyst. This new methodology has been successfully applied to a variety of α- or β-mono-, di-, and poly-thiosugar derivatives to efficiently synthesize a series of α- or β-N,S-bis-glycosyl quinolin-2-ones, which are difficult to synthesize by classical methods. Full article
(This article belongs to the Special Issue Glycomimetics: Design, Synthesis and Therapeutic Applications)
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