Difunctionalization of the Isocyano Group: Atom-Economic ­Synthesis of Pyrimidinediones

Synlett ◽  
2018 ◽  
Vol 30 (03) ◽  
pp. 252-256 ◽  
Author(s):  
Jian Lang ◽  
Ye Wei
Keyword(s):  
Late Stage ◽  
Functional Group ◽  
Structural Diversity ◽  
Synthetic Methods ◽  
Chemical Bonds ◽  
Atom Economy

The exploration of synthetic methods involving the formation of new chemical bonds at both the nitrogen and carbons atoms of the isocyano group would largely enrich the structural diversity of compounds. Herein, we disclosed a silver-catalyzed difunctionalization of the isocyano group with cyclic oximes. This method can generate a great array of structurally novel and interesting pyrimidinediones and features excellent atom economy, good functional group compatibility, and amenability to late-stage modifications.

Electrophilic Amination with Anthranils through Thioamide-Assisted Cobalt(III)-Catalyzed C(sp3)–H Activation

Synthesis ◽  
2020 ◽  
Vol 52 (24) ◽  
pp. 3881-3890
Author(s):  
Jie Li ◽  
Lei Liu ◽  
Zhao Zhang ◽  
Yucheng Wang ◽  
Yan Zhang
Keyword(s):  
Late Stage ◽  
Functional Group ◽  
Atom Economy ◽  
Electrophilic Amination ◽  
Amino Aldehydes ◽  
Mild Conditions ◽  
Weakly Coordinating

Cobalt(III)-catalyzed electrophilic amination of inert C(sp3)–H bonds of weakly coordinating thioamides with readily accessible anthranil derivatives was accomplished under mild conditions, with good functional group tolerance, thus providing various amino aldehydes and amino ketones. Moreover, our protocol with the versatile [Cp*Co(MeCN)3][SbF6]2 features excellent atom-economy and oxidant-free conditions, and allows facile late-stage functionalization.

Asymmetric Synthesis of α-Alkylated γ-Lactam via Nickel/8-Quinim-Catalyzed Reductive Alkyl-Carbamoylation of Unactivated Alkene

Synlett ◽  
2021 ◽  
Author(s):  
Xianqing Wu ◽  
Mohini Shrestha ◽  
Yifeng Chen
Keyword(s):  
Functional Group ◽  
Enantioselective Synthesis ◽  
Chiral Auxiliary ◽  
Alkyl Iodide ◽  
General Strategy ◽  
Chemical Bonds ◽  
Mild Conditions ◽  
Chiral Carbon ◽  
Enantioselective Reaction ◽  
Metal Catalyzed

AbstractChiral-auxiliary-mediated synthesis represents the most frequently used synthetic tool for the induction of chirality on α-position of γ-lactams in organic synthesis. However, the general strategy requires the stoichiometric use of chiral reagents with multiple manipulation steps. Transition-metal-catalyzed asymmetric alkene dicarbofunctionalization using readily available substrates under mild conditions allows the simultaneous construction of two vicinal chemical bonds and a chiral carbon center, hence, gain expedient access to chiral heterocycles. Herein, we disclose a Ni-catalyzed enantioselective reaction of 3-butenyl carbamoyl chloride and primary alkyl iodide enabled by a newly designed chiral 8-quinoline imidazoline ligand (8-Quinim). This protocol features broad functional group tolerance and high enantioselectivities, achieving unprecedented synthesis of chiral nonaromatic heterocycles via catalytic reductive protocol.1 Introduction2 Development of 8-Quinim Ligand3 Nickel/8-Quinim-Catalyzed Enantioselective Synthesis of Chiral α-Alkylated γ-Lactam4 Conclusion and Outlook

Direct synthesis of indazole derivatives via Rh(iii)-catalyzed C–H activation of phthalazinones and allenes

2021 ◽  
Vol 19 (35) ◽  
pp. 7701-7705
Author(s):  
Chuanliu Yin ◽  
Tianshuo Zhong ◽  
Xiangyun Zheng ◽  
Lianghao Li ◽  
Jian Zhou ◽  
...  
Keyword(s):  
Catalytic System ◽  
Functional Group ◽  
Direct Synthesis ◽  
Atom Economy

An Rh(iii)-catalyzed annulation of phthalazinones and various allenes was developed, leading to the formation of indazole derivatives. This catalytic system exhibits excellent functional group tolerance and atom economy.

scholarly journals Modern Synthetic Methods for the Stereoselective Construction of 1,3-Dienes

Molecules ◽  
2021 ◽  
Vol 26 (2) ◽  
pp. 249
Author(s):  
Raquel G. Soengas ◽  
Humberto Rodríguez-Solla
Keyword(s):  
Organic Chemistry ◽  
Natural Products ◽  
Functional Group ◽  
Biological Activities ◽  
Synthetic Methods ◽  
Bond Forming ◽  
Drug Candidates ◽  
The Past ◽  
Wide Range

The 1,3-butadiene motif is widely found in many natural products and drug candidates with relevant biological activities. Moreover, dienes are important targets for synthetic chemists, due to their ability to give access to a wide range of functional group transformations, including a broad range of C-C bond-forming processes. Therefore, the stereoselective preparation of dienes have attracted much attention over the past decades, and the search for new synthetic protocols continues unabated. The aim of this review is to give an overview of the diverse methodologies that have emerged in the last decade, with a focus on the synthetic processes that meet the requirements of efficiency and sustainability of modern organic chemistry.

C(sp3)–H Functionalization with Isocyanides

2021 ◽  
Author(s):  
Weixiang Wang ◽  
Tianqi Liu ◽  
Chang-Hua Ding ◽  
Bin Xu
Keyword(s):  
Functional Group ◽  
Ugi Reaction ◽  
Atom Economy ◽  
Passerini Reaction

Isocyanide is well known for its multi-component reactions (MCR), such as Passerini reaction and Ugi reaction, with diverse molecular skeletons, high functional group compatibility, and good atom economy. With the...

Uncatalyzed diastereoselective synthesis of alkyliminofurochromone-derived benzylmalononitriles via a three-component cascade reaction: competition between Diels–Alder cycloaddition and Michael addition

2021 ◽  
Author(s):  
Mohammad Bagher Teimouri ◽  
Zahra Mokhtare ◽  
Hamid Reza Khavasi
Keyword(s):  
Michael Addition ◽  
Heterocyclic Ring ◽  
Cascade Reaction ◽  
Diels Alder ◽  
Chemical Bonds ◽  
Diastereoselective Synthesis ◽  
Atom Economy ◽  
One Pot

Three new chemical bonds and three stereogenic centres and one heterocyclic ring were assembled stereoselectively in a convenient high atom-economy one-pot operation.

Asymmetric Hydrogenation of O-/N-Functional Group Substituted Arenes

2021 ◽  
Author(s):  
bingru shao ◽  
Lei Shi ◽  
Yong-Gui Zhou
Keyword(s):  
Natural Products ◽  
Functional Group ◽  
Asymmetric Hydrogenation ◽  
Biologically Active ◽  
Synthetic Methods

Asymmetric hydrogenation of aromatical compouds represents one of the most straightforward synthetic methods to construct important chiral cyclic skeletons that are often found in biologically active agents and natural products....

scholarly journals Nickel-Catalyzed Three-Component Olefin Reductive Dicarbofunctionalization to Access Highly Functionalized Alkylborates

2020 ◽  
Author(s):  
Xiao-Xu Wang ◽  
Xi Lu ◽  
Shi-Jiang He ◽  
Yao Fu
Keyword(s):  
Natural Products ◽  
Late Stage ◽  
Functional Group ◽  
Coupling Efficiency ◽  
Convergent Synthesis ◽  
Drug Molecules ◽  
Aryl Iodides ◽  
Alkyl Bromides ◽  
Vinyl Boronates ◽  
Convenient Access

We report a three-component olefin reductive dicarbofunctionalization for constructing densely functionalized alkylborates, specifically, nickel-catalyzed reductive dialkylation and alkylarylation of vinyl boronates with a variety of alkyl bromides and aryl iodides. This reaction exhibits good coupling efficiency and excellent functional group compatibility, providing convenient access to the late-stage modification of complex natural products and drug molecules. Combined with versatile alkylborate transformations, this reaction could also find applications in the modular and convergent synthesis of complex, densely functionalized compounds.

7-Azaindolyl- and indolyl-functionalized starburst molecules with a 1,3,5-triazine or a benzene core — Syntheses and luminescence

2006 ◽  
Vol 84 (4) ◽  
pp. 477-485 ◽  
Author(s):  
Wei-Hua Huang ◽  
Wen-Li Jia ◽  
Suning Wang
Keyword(s):  
Quantum Efficiency ◽  
Functional Group ◽  
Energy Gap ◽  
Central Core ◽  
Synthetic Methods ◽  
Coupling Reactions ◽  
Lumo Energy ◽  
Emission Energy ◽  
New Compounds ◽  
Homo Lumo

The syntheses of several new 7-azaindolyl-, indolyl-, and 3-methylindolyl-functionalized starburst molecules that contain either a 1,3,5-triazine, a benzene, a 2,4,6-triphenyl-2,4,6-triazine, a 1,3,5-triphenylbenzene, a 2,4,6-tris(biphenyl)-1,3,5-triazine, or a 1,3,5-tris(biphenyl)benzene core have been achieved. The synthetic methods used for these new compounds involve mostly Ullmann condensation and Suzuki coupling reactions. The thermal properties of the new molecules have been found to be highly dependent on the molecular weight and the central core. Glass transition temperatures greater than 150 °C were observed for the large starburst molecules based on the 2,4,6-tris(biphenyl)-1,3,5-triazine or the 1,3,5-tris(biphenyl)benzene core. The new starburst molecules are luminescent in the violet-blue region in solution and in the solid state. The emission energy and the quantum efficiency were found to be highly dependent on the central core and the functional group. In general, the triazine-based molecules were found to have a smaller HOMO–LUMO energy gap than the benzene-based analogues. The triphenyltriazine- or triphenylbenzene-based molecules were found to display a higher emission quantum efficiency than the large tris(biphenyl)triazine- or tris(biphenyl)benzene-based molecules.Key words: 7-azaindolyl, indolyl derivative, triazine and benzene cores, starburst molecule, blue luminescence.

scholarly journals Tyrosine and Drug-like Late-stage Benzylic Functionalization via Photoredox Catalysis

2020 ◽  
Author(s):  
Tobias Brandhofer ◽  
Volker Derdau ◽  
María Mendez ◽  
Christoph Pöverlein ◽  
Olga Garcia Mancheno
Keyword(s):  
Natural Products ◽  
Visible Light ◽  
Late Stage ◽  
Medicinal Chemistry ◽  
Functional Group ◽  
Reaction Conditions ◽  
Site Selectivity ◽  
Wide Range ◽  
High Yields ◽  
Therapeutic Compounds

Abstract Visible light mediated late-stage functionalization is a rising field in synthetic and medicinal chemistry, allowing the fast and diversified modification of valuable, potentially therapeutic compounds such as peptides. However, there are relatively few mild methodologies for the C(sp3)-H functionalization of complex peptides. Herein, we report a visible light mediated photocatalytic protocol for the benzylic C-H modification of tyrosine and related C-H bonds. The embraced radical-cation/deprotonation strategy enables an incorporation of a wide range of valuable functional groups in high yields and chemoselectivity. The mild reaction conditions, site-selectivity and high functional group tolerance was highlighted by the functionalization of complex peptides, drugs and natural products, providing a promising synthetic platform in medicinal chemistry.

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