Cyclopropyl Building Blocks for Organic Synthesis. Part 85. Facile Preparation and Chemical Transformations of Spirocyclopropane-Anellated Heterocycles.

AbstractEnaminones are gaining increasing interest because of their unique properties and their importance in organic synthesis as versatile building blocks. N,N-Dimethyl enaminones offer a better leaving group (a dimethylamine group) than other enaminones, and allow further elaboration via a range of facile chemical transformations. Over the past five years, there have been an increasing number of reports describing the synthetic applications of N,N-dimethyl enaminones. This review provides a comprehensive overview on the synthetic applications of N,N-dimethyl enaminones that have been reported since 2016.1 Introduction2 Direct C(sp2)–H α-Functionalization2.1 Synthesis of α-Sulfenylated N,N-Dimethyl Enaminones2.2 Synthesis of α-Thiocyanated N,N-Dimethyl Enaminones2.3 Synthesis of α-Acyloxylated N,N-Dimethyl Enaminones3 Functionalization Reactions via C=C Double Bond Cleavage3.1 Synthesis of Functionalized Methyl Ketones3.2 Synthesis of α-Ketoamides, α-Ketoesters and 1,2-Diketones3.3 Synthesis of N-Sulfonyl Amidines4 Construction of All-Carbon Aromatic Scaffolds4.1 Synthesis of Benzaldehydes4.2 Synthesis of the Naphthalenes5 Construction of Heterocyclic Scaffolds5.1 Synthesis of Five-Membered Heterocycles5.2 Synthesis of Six-Membered Heterocycles5.3 Synthesis of Quinolines 5.4 Synthesis of Functionalized Chromones5.5 Synthesis of Other Fused Polycyclic Heterocycles6 Conclusions and Perspectives

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Five-Membered Cyclic Carbonates: Versatility for Applications in Organic Synthesis, Pharmaceutical, and Materials Sciences

Applied Sciences ◽

10.3390/app11115024 ◽

2021 ◽

Vol 11 (11) ◽

pp. 5024

Author(s):

Patrick Rollin ◽

Liane K. Soares ◽

Angelita M. Barcellos ◽

Daniela R. Araujo ◽

Eder J. Lenardão ◽

...

Keyword(s):

Organic Synthesis ◽

Flame Retardants ◽

Building Blocks ◽

Chemical Transformations ◽

Cyclic Carbonates ◽

Recent Advances ◽

Important Chemical ◽

Biological Potential

This review presents the recent advances involving several applications of five-membered cyclic carbonates and derivatives. With more than 150 references, it covers the period from 2012 to 2020, with special emphasis on the use of five-membered cyclic carbonates as building blocks for organic synthesis and material elaboration. We demonstrate the application of cyclic carbonates in several important chemical transformations, such as decarboxylation, hydrogenation, and transesterification reactions, among others. The presence of cyclic carbonates in molecules with high biological potential is also displayed, together with the importance of these compounds in the preparation of materials such as urethanes, polyurethanes, and flame retardants.

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C-1 Building Blocks in Organic Synthesis 1

10.1055/b-003-125818 ◽

2014 ◽

Cited By ~ 1

Keyword(s):

Organic Synthesis ◽

Building Blocks

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

10.26434/chemrxiv.7961633.v1 ◽

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 α-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 α-aminoboronates via 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.

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Thienopyrrolocarbazoles: New Building Blocks for Functional Organic Materials

10.26434/chemrxiv.7777343.v1 ◽

2019 ◽

Cited By ~ 1

Author(s):

Dorian Bader ◽

Johannes Fröhlich ◽

Paul Kautny

Keyword(s):

Building Block ◽

Organic Materials ◽

Building Blocks ◽

Molecular Properties ◽

The Family ◽

Facile Preparation

The facile preparation of three regioisomeric thienopyrrolocarbazoles applying a convenient C-H activation approach is presented. Derived from indolo[3,2,1-jk]carbazole, the incorporation of thiophene into the triarylamine framework significantly impacted the molecular properties of the parent scaffold. The developed thienopyrrolocarbazoles enrich the family of triarylamine donors and constitute a novel building block for functional organic materials.

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Thienopyrrolocarbazoles: New Building Blocks for Functional Organic Materials

10.26434/chemrxiv.7777343 ◽

2019 ◽

Author(s):

Dorian Bader ◽

Johannes Fröhlich ◽

Paul Kautny

Keyword(s):

Building Block ◽

Organic Materials ◽

Building Blocks ◽

Molecular Properties ◽

The Family ◽

Facile Preparation

The facile preparation of three regioisomeric thienopyrrolocarbazoles applying a convenient C-H activation approach is presented. Derived from indolo[3,2,1-jk]carbazole, the incorporation of thiophene into the triarylamine framework significantly impacted the molecular properties of the parent scaffold. The developed thienopyrrolocarbazoles enrich the family of triarylamine donors and constitute a novel building block for functional organic materials.

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Electrochemical Oxidative Esterification of Thiophenols: Efficient Access to Sulfinic Esters

Current Organic Synthesis ◽

10.2174/1570179417666200620215704 ◽

2020 ◽

Vol 17 (7) ◽

pp. 540-547

Author(s):

Chun-Hui Yang ◽

Cheng Wu ◽

Jun-Ming Zhang ◽

Xiang-Zhang Tao ◽

Jun Xu ◽

...

Keyword(s):

Organic Synthesis ◽

Efficient Method ◽

High Efficiency ◽

Building Blocks ◽

Constant Current ◽

Good Efficiency ◽

Oxidative Esterification ◽

Efficient Access ◽

New Applications ◽

Sulfinic Esters

Background: The sulfinic esters are important and useful building blocks in organic synthesis. Objective: The aim of this study was to develop a simple and efficient method for the synthesis of sulfinic esters. Materials and Methods: Constant current electrolysis from thiols and alcohols was selected as the method for the synthesis of sulfinic esters. Results and Discussion: A novel electrochemical method for the synthesis of sulfinic esters from thiophenols and alcohols has been developed. Up to 27 examples of sulfinic esters have been synthesized using the current methods. This protocol shows good functional group tolerance as well as high efficiency. In addition, this protocol can be easily scaled up with good efficiency. Notably, heterocycle-containing substrates, including pyridine, thiophene, and benzothiazole, gave the desired products in good yields. A plausible reaction mechanism is proposed. Conclusion: This research not only provides a green and efficient method for the synthesis of sulfinic esters but also shows new applications of electrochemistry in organic synthesis. It is considered that this green and efficient synthetic protocol used to prepare sulfinic esters will have good applications in the future.

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