Catalytic, Enantioselective Syn-Diamination of Alkenes

2019 ◽  
Author(s):  
Zhonglin Tao ◽  
Brad Gilbert ◽  
Scott Denmark
Keyword(s):  
General Solution ◽  
Organic Synthesis ◽  
Medicinal Chemistry ◽  
Catalytic Cycle ◽  
Bifunctional Nucleophile

The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A general solution to this problem would enable the efficient and selective preparation of widely useful, enantioenriched diamines for applications in medicinal chemistry and catalysis. In this Article we describe the first enantioselective, <i>syn-</i>diamination of simple alkenes mediated by a chiral, enantioenriched organoselenium catalyst together with a <i>N,N’-</i>bistosyl urea as the bifunctional nucleophile and <i>N-</i>fluorocollidinium tetrafluoroborate as the stoichiometric oxidant. Diaryl, aryl-alkyl, and alkyl-alkyl olefins bearing a variety of substituents are all diaminated in consistently high enantioselectivities selectivities but variable yields. The reaction likely proceeds through a Se(II)/Se(IV) redox catalytic cycle reminiscent of the <i>syn-</i>dichlorination reported previously. Furthermore, the <i>syn</i>-stereospecificity of the transformation shows promise for highly enantioselective diaminations of alkenes with no strong steric or electronic bias.

Catalytic, Enantioselective Syn-Diamination of Alkenes

2019 ◽  
Author(s):  
Zhonglin Tao ◽  
Brad Gilbert ◽  
Scott Denmark
Keyword(s):  
General Solution ◽  
Organic Synthesis ◽  
Medicinal Chemistry ◽  
Catalytic Cycle ◽  
Bifunctional Nucleophile

The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A general solution to this problem would enable the efficient and selective preparation of widely useful, enantioenriched diamines for applications in medicinal chemistry and catalysis. In this Article we describe the first enantioselective, <i>syn-</i>diamination of simple alkenes mediated by a chiral, enantioenriched organoselenium catalyst together with a <i>N,N’-</i>bistosyl urea as the bifunctional nucleophile and <i>N-</i>fluorocollidinium tetrafluoroborate as the stoichiometric oxidant. Diaryl, aryl-alkyl, and alkyl-alkyl olefins bearing a variety of substituents are all diaminated in consistently high enantioselectivities selectivities but variable yields. The reaction likely proceeds through a Se(II)/Se(IV) redox catalytic cycle reminiscent of the <i>syn-</i>dichlorination reported previously. Furthermore, the <i>syn</i>-stereospecificity of the transformation shows promise for highly enantioselective diaminations of alkenes with no strong steric or electronic bias.

Cascade CuH-Catalyzed Conversion of Alkynes to Enantioenriched 1,1-Disubstituted Products

2019 ◽  
Author(s):  
De-Wei Gao ◽  
Yang Gao ◽  
Huiling Shao ◽  
Tian-Zhang Qiao ◽  
Xin Wang ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Medicinal Chemistry ◽  
Proteasome Inhibitors ◽  
Building Blocks ◽  
Unique Role ◽  
Efficient Strategy ◽  
Carbon Centers ◽  
Rapid Access ◽  
Cascade Catalysis ◽  
Privileged Scaffolds

Enantioenriched <i>α</i>-aminoboronic acids play a unique role in medicinal chemistry and have emerged as privileged pharmacophores in proteasome inhibitors. Additionally, they represent synthetically useful chiral building blocks in organic synthesis. Recently, CuH-catalyzed asymmetric alkene hydrofunctionalization has become a powerful tool to construct stereogenic carbon centers. In contrast, applying CuH cascade catalysis to achieve reductive 1,1-difunctionalization of alkynes remains an important, but largely unaddressed, synthetic challenge. Herein, we report an efficient strategy to synthesize <i>α</i>-aminoboronates <i>via </i>CuH-catalyzed hydroboration/hydroamination cascade of readily available alkynes. Notably, this transformation selectively delivers the desired 1,1-heterodifunctionalized product in favor of alternative homodifunctionalized, 1,2-heterodifunctionalized, or reductively monofunctionalized byproducts, thereby offering rapid access to these privileged scaffolds with high chemo-, regio- and enantioselectivity.<br>

Construction of N-heterocycles via Pd-mediated C–H activation/annulation strategies

2022 ◽  
Author(s):  
Mengyu Qiu ◽  
Xuegang Fu ◽  
Peng Fu ◽  
Jianhui Huang
Keyword(s):  
Natural Products ◽  
Organic Synthesis ◽  
Material Science ◽  
Medicinal Chemistry ◽  
Drug Molecules

N-heterocycles can be found in natural products and drug molecules, which are indispensable components in the area of organic synthesis, medicinal chemistry and material science. The construction of these N-containing...

Ethenesulfonyl Fluoride (ESF) and Its Derivatives in SuFEx Click Chemistry and More

Synthesis ◽  
2019 ◽  
Vol 52 (05) ◽  
pp. 673-687 ◽  
Author(s):  
Yan-Ping Meng ◽  
Shi-Meng Wang ◽  
Wan-Yin Fang ◽  
Zhi-Zhong Xie ◽  
Jing Leng ◽  
...  
Keyword(s):  
Organic Chemistry ◽  
Click Chemistry ◽  
Exchange Reaction ◽  
Organic Synthesis ◽  
Medicinal Chemistry ◽  
Materials Science ◽  
Click Reaction ◽  
Chemical Properties ◽  
Chemical Transformations ◽  
Absolute Reliability

The sulfur(VI) fluoride exchange reaction (SuFEx), developed by Sharpless and co-workers in 2014, is a new category of click reaction that creates molecular connections with absolute reliability and unprecedented efficiency through a sulfur(VI) hub. Ethenesulfonyl fluoride (ESF), as one of the most important sulfur(VI) hubs, exhibits extraordinary reactivity in SuFEx click chemistry and organic synthesis. This review summarizes the chemical properties and applications of ESF in click chemistry, organic chemistry, materials science, medicinal chemistry and in many other fields related to organic synthesis.1 Introduction2 Chemical Transformations of ESF3 Chemical Transformations of 2-Arylethenesulfonyl Fluorides4 Novel SuFEx Reagents Derived from ESF5 Applications of ESF Derivatives in Medicinal Chemistry6 Applications of ESF Derivatives in Materials Science7 Conclusion

scholarly journals Revisiting the Structure and Chemistry of 3(5)-Substituted Pyrazoles

Molecules ◽  
2019 ◽  
Vol 25 (1) ◽  
pp. 42 ◽  
Author(s):  
Alina Secrieru ◽  
Paul Michael O’Neill ◽  
Maria Lurdes Santos Cristiano
Keyword(s):  
Organic Synthesis ◽  
Medicinal Chemistry ◽  
Positive Impact ◽  
Biological Activities ◽  
Experimental Methods ◽  
Synthetic Methods ◽  
Conformational Preferences ◽  
Substituted Pyrazoles ◽  
Present Subject

Pyrazoles are known as versatile scaffolds in organic synthesis and medicinal chemistry, often used as starting materials for the preparation of more complex heterocyclic systems with relevance in the pharmaceutical field. Pyrazoles are also interesting compounds from a structural viewpoint, mainly because they exhibit tautomerism. This phenomenon may influence their reactivity, with possible impact on the synthetic strategies where pyrazoles take part, as well as on the biological activities of targets bearing a pyrazole moiety, since a change in structure translates into changes in properties. Investigations of the structure of pyrazoles that unravel the tautomeric and conformational preferences are therefore of upmost relevance. 3(5)-Aminopyrazoles are largely explored as precursors in the synthesis of condensed heterocyclic systems, namely pyrazolo[1,5-a]pyrimidines. However, the information available in the literature concerning the structure and chemistry of 3(5)-aminopyrazoles is scarce and disperse. We provide a revision of data on the present subject, based on investigations using theoretical and experimental methods, together with the applications of the compounds in synthesis. It is expected that the combined information will contribute to a deeper understanding of structure/reactivity relationships in this class of heterocycles, with a positive impact in the design of synthetic methods, where they take part.

Advances in the Synthesis of Isatins: A Survey of the Last Decade

Synthesis ◽  
2018 ◽  
Vol 50 (08) ◽  
pp. 1601-1609 ◽  
Author(s):  
Andrei Bogdanov ◽  
Vladimir Mironov
Keyword(s):  
Organic Synthesis ◽  
Medicinal Chemistry ◽  
Indole Derivatives ◽  
Isatin Derivatives

Isatin derivatives are widely used in organic synthesis, in medicinal chemistry and in the chemistry of materials. This report summarizes modern trends in the synthesis of substituted indolin-2,3-diones covering the literature from 2007 to 2017. Studies on the influence of the structure of substituents in the initial substrates on the formation of the heterocyclic isatin system and the yields of the target compounds are also discussed.1 Introduction2 Oxidation of Indole Derivatives3 Cyclization of o-Aminoacetophenones4 Cyclization of N-Acylanilines5 Miscellaneous6 Conclusion

An Efficient Cascade Synthesis of Ethyl 3-Amino-5-oxoisoxazolidine-4-carboxylate Derivatives

Synthesis ◽  
2017 ◽  
Vol 49 (18) ◽  
pp. 4341-4349
Author(s):  
Runtao Li ◽  
Runrun Li ◽  
Qiang Wei ◽  
Xin Wang ◽  
Zemei Ge
Keyword(s):  
Organic Synthesis ◽  
Medicinal Chemistry ◽  
Wide Range

An efficient cascade synthesis of ethyl 3-amino-5-oxoisoxa­zolidine-4-carboxylate derivatives from diethyl 2-(ethoxymethyl­ene)malonate, different hydroxylamines and various amines is developed. This approach tolerates a wide range of amines affording highly functionalized isoxazolidine derivatives, which are expected to be important in organic synthesis and medicinal chemistry.

scholarly journals Synthetic Strategies in the Preparation of Phenanthridinones

Molecules ◽  
2021 ◽  
Vol 26 (18) ◽  
pp. 5560
Author(s):  
Rajeshwar Reddy Aleti ◽  
Alexey A. Festa ◽  
Leonid G. Voskressensky ◽  
Erik V. Van der Eycken
Keyword(s):  
Natural Products ◽  
Organic Synthesis ◽  
Medicinal Chemistry ◽  
Coupling Reactions ◽  
Structural Importance ◽  
Wide Range ◽  
Biaryl Coupling ◽  
Synthetic Methodologies

Phenanthridinones are important heterocyclic frameworks present in a variety of complex natural products, pharmaceuticals and displaying wide range of pharmacological actions. Its structural importance has evoked a great deal of interest in the domains of organic synthesis and medicinal chemistry to develop new synthetic methodologies, as well as novel compounds of pharmaceutical interest. This review focuses on the synthesis of phenanthridinone scaffolds by employing aryl-aryl, N-aryl, and biaryl coupling reactions, decarboxylative amidations, and photocatalyzed reactions.

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