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.

Regiospecific Palladium-Catalyzed Cross-Coupling Reactions Using the Operational Equivalent of 1,3-Dilithiopropyne

Synthesis ◽  
2020 ◽  
Vol 52 (16) ◽  
pp. 2387-2394 ◽  
Author(s):  
Jorge A. Cabezas ◽  
Natasha Ferllini
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Terminal Alkyne ◽  
Copper Iodide ◽  
Reaction Conditions ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Palladium Catalyzed ◽  
High Yields

A regiospecific palladium-catalyzed cross-coupling reaction using the operational equivalent of the dianion 1,3-dilithiopropyne, with aromatic iodides is reported. This reaction gives high yields of 1-propyn-1-yl-benzenes and 2-(propyn-1-yl)thiophenes in the presence of catalytic amounts of palladium(0) or (II) and stoichiometric amounts of copper iodide. No terminal alkyne or allene isomers were detected. Reaction conditions were very mild and several functional groups were tolerated.

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

scholarly journals Computational Insights into Intramolecular Cross-Coupling of Quaternary Borate Salts

2021 ◽  
Author(s):  
Florian Matz ◽  
Arif Music ◽  
Dorian Didier ◽  
Thomas C. Jagau
Keyword(s):  
Organic Synthesis ◽  
Energy Barrier ◽  
Density Functional ◽  
Bond Formation ◽  
Cross Coupling ◽  
Coupled Cluster ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Product Distributions ◽  
Borate Salts

Cross-coupling reactions for C-C bond formation represent a cornerstone of organic synthesis. In most cases, they make use of transition metals, which has several downsides. Recently, metal-free alternatives relying on electrochemistry have gained interest. One example of such a reaction is the oxidation of tetraorganoborate salts that initiates aryl-aryl and aryl-alkenyl couplings with promising selectivities. This work investigates the mechanism of this reaction computationally using density functional and coupled-cluster theory. Our calculations reveal a distinct difference between aryl-alkenyl and aryl-aryl couplings: While C-C bond formation occurs irreversibly and without an energy barrier if an alkenyl residue is involved, many intermediates can be identified in aryl-aryl couplings. In the latter case, intramolecular transitions between reaction paths leading to different products are possible. Based on the energy differences between these intermediates, we develop a kinetic model to estimate product distributions for aryl-aryl couplings.<br>

scholarly journals Computational Insights into Intramolecular Cross-Coupling of Quaternary Borate Salts

2021 ◽  
Author(s):  
Florian Matz ◽  
Arif Music ◽  
Dorian Didier ◽  
Thomas C. Jagau
Keyword(s):  
Organic Synthesis ◽  
Energy Barrier ◽  
Density Functional ◽  
Bond Formation ◽  
Cross Coupling ◽  
Coupled Cluster ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Product Distributions ◽  
Borate Salts

Cross-coupling reactions for C-C bond formation represent a cornerstone of organic synthesis. In most cases, they make use of transition metals, which has several downsides. Recently, metal-free alternatives relying on electrochemistry have gained interest. One example of such a reaction is the oxidation of tetraorganoborate salts that initiates aryl-aryl and aryl-alkenyl couplings with promising selectivities. This work investigates the mechanism of this reaction computationally using density functional and coupled-cluster theory. Our calculations reveal a distinct difference between aryl-alkenyl and aryl-aryl couplings: While C-C bond formation occurs irreversibly and without an energy barrier if an alkenyl residue is involved, many intermediates can be identified in aryl-aryl couplings. In the latter case, intramolecular transitions between reaction paths leading to different products are possible. Based on the energy differences between these intermediates, we develop a kinetic model to estimate product distributions for aryl-aryl couplings.<br>

scholarly journals Borylation and rearrangement of alkynyloxiranes: a stereospecific route to substituted α-enynes

2019 ◽  
Vol 15 ◽  
pp. 1416-1424
Author(s):  
Ruben Pomar Fuentespina ◽  
José Angel Garcia de la Cruz ◽  
Gabriel Durin ◽  
Victor Mamane ◽  
Jean-Marc Weibel ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Cross Coupling ◽  
Functional Materials ◽  
Building Blocks ◽  
Cascade Process ◽  
Coupling Reactions ◽  
One Pot ◽  
Bioactive Natural Products ◽  
Cross Coupling Reactions ◽  
Synthetic Approaches

1,3-Enynes are important building blocks in organic synthesis and also constitute the key motif in various bioactive natural products and functional materials. However, synthetic approaches to stereodefined substituted 1,3-enynes remain a challenge, as they are limited to Wittig and cross-coupling reactions. Herein, stereodefined 1,3-enynes, including tetrasubstituted ones, were straightforwardly synthesized from cis or trans-alkynylated oxiranes in good to excellent yields by a one-pot cascade process. The procedure relies on oxirane deprotonation, borylation and a stereospecific rearrangement of the so-formed alkynyloxiranyl borates. This stereospecific process overall transfers the cis or trans-stereochemistry of the starting alkynyloxiranes to the resulting 1,3-enynes.

Application of Palladium-Catalyzed Cross-Coupling Reactions in Organic Synthesis

2020 ◽  
Vol 16 (8) ◽  
pp. 1105-1142 ◽  
Author(s):  
Shalu Sain ◽  
Sonika Jain ◽  
Manish Srivastava ◽  
Rajendra Vishwakarma ◽  
Jaya Dwivedi
Keyword(s):  
Organic Synthesis ◽  
Heterocyclic Compounds ◽  
Cross Coupling ◽  
Present Review ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Palladium Catalyzed

: Palladium-catalyzed cross-coupling reactions have gained a continuously growing interest of synthetic organic chemists. The present review gives a brief account of applications of the palladium-catalyzed cross-coupling reactions in comprehensive synthesis, viz., the Heck, Stille, Suzuki–Miyaura, Negishi, Sonogashira, Buchwald–Hartwig, Ullmann and the Oxidative, decarboxylative cross-coupling reactions, with particular emphasis on the synthesis of heterocyclic compounds.

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