Pharmaceutical diversification via palladium oxidative addition complexes

Science ◽  
2019 ◽  
Vol 363 (6425) ◽  
pp. 405-408 ◽  
Author(s):  
Mycah R. Uehling ◽  
Ryan P. King ◽  
Shane W. Krska ◽  
Tim Cernak ◽  
Stephen L. Buchwald
Keyword(s):  
Chemical Space ◽  
Oxidative Addition ◽  
Cross Coupling ◽  
Catalytic Reactions ◽  
Coupling Reactions ◽  
Chemical Probes ◽  
Ambient Conditions ◽  
Cross Coupling Reactions ◽  
Alternative Approach ◽  
Palladium Catalyzed

Palladium-catalyzed cross-coupling reactions have transformed the exploration of chemical space in the search for materials, medicines, chemical probes, and other functional molecules. However, cross-coupling of densely functionalized substrates remains a major challenge. We devised an alternative approach using stoichiometric quantities of palladium oxidative addition complexes (OACs) derived from drugs or drug-like aryl halides as substrates. In most cases, cross-coupling reactions using OACs proceed under milder conditions and with higher success than the analogous catalytic reactions. OACs exhibit remarkable stability, maintaining their reactivity after months of benchtop storage under ambient conditions. We demonstrated the utility of OACs in a variety of experiments including automated nanomole-scale couplings between an OAC derived from rivaroxaban and hundreds of diverse nucleophiles, as well as the late-stage derivatization of the natural product k252a.

scholarly journals New trends in the cross-coupling and other catalytic reactions

2017 ◽  
Vol 89 (10) ◽  
pp. 1413-1428 ◽  
Author(s):  
Irina P. Beletskaya ◽  
Alexei D. Averin
Keyword(s):  
Lewis Acids ◽  
Bond Formation ◽  
Cross Coupling ◽  
Pd Nanoparticles ◽  
Catalytic Reactions ◽  
Coupling Reactions ◽  
Ch Activation ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed ◽  
Catalyzed Reactions

AbstractA mini-review covers the latest achievements in the field of metal-mediated cross-coupling reactions among which are palladium-catalyzed Heck, Suzuki, cyanation and amination reactions. The aspects of the application of Pd nanoparticles (PdNPs) are discussed. The possibilities of the applications of Cu(I)-catalyzed reactions are described. Special emphasis is made on the synthesis of polymacrocyclic compounds like porphyrin dyads and triads, polyazacryptands bearing fluorophore groups using catalytic methods. The application of Pd-catalyzed CH-activation reactions for porphyrin modifications is described, the use of Lewis acids catalysis and organocatalysis for enantioselective C–C bond formation is considered with the emphasis on the application of immobilized organocatalyst.

scholarly journals Palladium-catalyzed highly regioselective mono and double Sonogashira cross-coupling reactions of 5-substituted-1,2,3-triiodobenzene under ambient conditions

RSC Advances ◽  
2020 ◽  
Vol 10 (28) ◽  
pp. 16366-16376
Author(s):  
Raed M. Al-Zoubi ◽  
Mothana K. Al-Omari ◽  
Walid K. Al-Jammal ◽  
Michael J. Ferguson
Keyword(s):  
Cross Coupling ◽  
Regioselective Synthesis ◽  
Coupling Reactions ◽  
Ambient Conditions ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed

Efficient and highly regioselective synthesis of 2,3-diiodinated diphenylacetylene and iodinated meta-terphenylacetylene derivatives via mono and double Sonogashira cross-coupling reactions.

Dual Nickel/Palladium-Catalyzed Reductive Cross-Coupling Reactions Between Two Phenol Derivatives

2020 ◽  
Author(s):  
Baojian Xiong ◽  
Yue Li ◽  
Yin Wei ◽  
Søren Kramer ◽  
Zhong Lian
Keyword(s):  
Functional Group ◽  
Low Cost ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Phenol Derivatives ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed ◽  
One Step ◽  
Aryl Tosylates ◽  
Low Sensitivity

Cross-coupling between substrates that can be easily derived from phenols is highly attractive due to the abundance and low cost of phenols. Here, we report a dual nickel/palladium-catalyzed reductive cross-coupling between aryl tosylates and aryl triflates; both substrates can be accessed in just one step from readily available phenols. The reaction has a broad functional group tolerance and substrate scope (>60 examples). Furthermore, it displays low sensitivity to steric effects demonstrated by the synthesis of a 2,2’disubstituted biaryl and a fully substituted aryl product. The widespread presence of phenols in natural products and pharmaceuticals allow for straightforward late-stage functionalization, illustrated with examples such as Ezetimibe and tyrosine. NMR spectroscopy and DFT calculations indicate that the nickel catalyst is responsible for activating the aryl triflate, while the palladium catalyst preferentially reacts with the aryl tosylate.

Formal Total Syntheses of Crocacin A-D

2005 ◽  
Vol 70 (10) ◽  
pp. 1696-1708 ◽  
Author(s):  
Magnus Besev ◽  
Christof Brehm ◽  
Alois Fürstner
Keyword(s):  
Natural Products ◽  
Aldol Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Total Syntheses ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed ◽  
The Common ◽  
Selective Addition

A concise route to the common polyketide fragment5of crocacin A-D (1-4) is presented which has previously been converted into all members of this fungicidal and cytotoxic family of dipeptidic natural products by various means. Our synthesis features asyn-selective titanium aldol reaction controlled by a valinol-derived auxiliary, a zinc-mediated, palladium-catalyzedanti-selective addition of propargyl mesylate10to the chiral aldehyde9, as well as a comparison of palladium-catalyzed Stille and Suzuki cross-coupling reactions for the formation of the diene moiety of the target.

Base-Free Synthesis and Synthetic Application of Novel 3-(organochalcogenyl)prop-2-yn-1-yl Esters: Promising Anticancer Agents

Synthesis ◽  
2021 ◽  
Author(s):  
Fabiane Gritzenco ◽  
Jean Carlo Kazmierczak ◽  
Thiago Anjos ◽  
Adriane Sperança ◽  
Maura Luise Bruckchem Peixoto ◽  
...  
Keyword(s):  
Anticancer Agents ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Chalcogen Bond ◽  
Cross Coupling Reactions ◽  
Air Atmosphere ◽  
Carbon Carbon Bonds ◽  
Palladium Catalyzed ◽  
Synthetic Application

This manuscript portrays the CuI-catalyzed Csp-chalcogen bond formation through cross-coupling reactions of propynyl esters and diorganyl dichalcogenides by using DMSO as solvent, at room temperature, under base-free and open-to-air atmosphere. Generally, the reactions have proceeded very smoothly, being tolerant to range of substituents present in both substrates, affording the novel 3-(organochalcogenyl)prop-2-yn-1-yl esters in moderate to good yields. Noteworthy, the 3-(butylselanyl)prop-2-yn-1-yl benzoate proved to be useful as synthetic precursor in palladium-catalyzed Suzuki and Sonogashira type cross-coupling reactions by replacing the carbon-chalcogen bond by new carbon-carbon bonds. Moreover, the 3-(phenylselanyl)prop-2-yn-1-yl benzoate has shown promising in vitro activity against glioblastoma cancer cells.

C -Glycosylated Phenylalanine Synthesis by Palladium-Catalyzed Cross-Coupling Reactions

Synlett ◽  
2003 ◽  
pp. 1834-1837 ◽  
Author(s):  
Nadège Lubin-Germain ◽  
Jacques Augé ◽  
Valérie Boucard ◽  
Karen Larrieu ◽  
Jacques Uziel
Keyword(s):  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed
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