scholarly journals Capturing the Most Active State of a Palladium(0) Cross-Coupling Catalyst

2021 ◽  
Author(s):  
Sii Hong Lau ◽  
Liye Chen ◽  
Illia Kevlishvili ◽  
Katherine Davis ◽  
Peng Liu ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Cryogenic Temperature ◽  
Active Form ◽  
Cross Coupling ◽  
Active Species ◽  
Palladium Complexes ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Solid State Characterization

Zerovalent palladium complexes are ubiquitous active species in modern cross-coupling reactions that comprise many premier methods for the construction of C–C and C–heteroatom bonds in organic synthesis. While palladium(0) complexes stabilized by two or more dative ligands are widely known, the most active form of Pd(0) coordinated by a single ancillary ligand (“monoligated Pd(0)”) has long eluded direct characterization. We report the synthesis and unambiguous solution- and solid-state characterization of functionally 12-electron Pd(0) complexes coordinated by a single tri(1-adamantyl)phosphine (PAd3) ligand. Access to these fleeting intermediates was achieved by enabling B-to-Pd transmetalation reactions that occur at cryogenic temperature. This work opens new avenues to experimentally interrogate highly reactive on-cycle Pd(0) catalysts and their structure-dependent reactivity and speciation, which should be broadly informative in continuing studies of catalytic processes featuring the prevalent Pd(0)/Pd(II) redox couple.

Cross-Coupling Reactions with 2-Amino-/Acetylamino-Substituted 3-Iodo-1,4-naphthoquinones: Convenient Synthesis of Novel Alkenyl- and Alkynylnaphthoquinones and Derivatives

Synthesis ◽  
2021 ◽  
Author(s):  
Felipe C. Demidoff ◽  
Leandro L. de Carvalho ◽  
Eduardo José P. Rodrigues Filho ◽  
Andréa Luzia F. de Souza ◽  
Chaquip D. Netto
Keyword(s):  
Click Chemistry ◽  
Organic Synthesis ◽  
Biological Activities ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Large Array ◽  
Terminal Alkyne ◽  
Co Catalyst ◽  
Cross Coupling Reactions ◽  
Convenient Synthesis

AbstractFunctionalized 1,4-naphthoquinones have been employed as versatile synthons in organic synthesis, in addition to presenting a large array of biological activities. Herein, the applications of 2-amino-/ acetylamino-substituted 3-iodo-1,4-naphthoquinones in cross-coupling reactions are described to successfully afford sixteen novel 3-styryl-1,4-naphthoquinones (amino-stilbene-quinone hybrids) and four 3-alkynyl-1,4-naphthoquinone in overall good yields. Interestingly, the alkynylated derivatives could be obtained from ligand- and Pd-free CuI-mediated cross-coupling reactions, after extensive investigations to exclude Pd as a co-catalyst. Lastly, the desilanized terminal alkyne was subjected to click chemistry reactions to give two novel triazole-1,4-naphthoquinone hybrids.

Recent Applications of Continuous Flow in Homogeneous Palladium Catalysis

Synthesis ◽  
2020 ◽  
Vol 52 (23) ◽  
pp. 3511-3529 ◽  
Author(s):  
Peter Koóš ◽  
Martin Markovič ◽  
Pavol Lopatka ◽  
Tibor Gracza
Keyword(s):  
Organic Synthesis ◽  
Continuous Flow ◽  
Palladium Catalysis ◽  
Flow Chemistry ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Flow Conditions ◽  
Cross Coupling Reactions ◽  
Continuous Flow Chemistry ◽  
Oxidative Transformations

Considerable advances have been made using continuous flow chemistry as an enabling tool in organic synthesis. Consequently, the number of articles reporting continuous flow methods has increased significantly in recent years. This review covers the progress achieved in homogeneous palladium catalysis using continuous flow conditions over the last five years, including C–C/C–N cross-coupling reactions, carbonylations and reductive/oxidative transformations.1 Introduction2 C–C Cross-Coupling Reactions3 C–N Coupling Reactions4 Carbonylation Reactions5 Miscellaneous Reactions6 Key to Schematic Symbols7 Conclusion

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