scholarly journals Photosensitized Nickel Catalysis Enabled Silyl Radical Mediated Direct Activation of Carbamoyl Chlorides to Access (Hetero)aryl Carbamides

2021 ◽  
Author(s):  
Sudip Maiti ◽  
Sayan Roy ◽  
Pintu Ghosh ◽  
Debabrata Maiti
Keyword(s):  
Structural Motif ◽  
Ni Catalyst ◽  
Nickel Catalysis ◽  
Metal Catalysis ◽  
Amide Bonds ◽  
Aryl Chlorides ◽  
Avant Garde ◽  
Silyl Radical ◽  
Direct Activation ◽  
Drug Molecules

The transformation of a readily available molecule to a medicinally relevant functionality is the heart of organic synthesis which literally unfolds new direction in the field of drug discovery and development. Accordingly, synthetic chemistry fraternity is constantly striving to introduce a range of avant-garde techniques to construct an incredibly important fundamental entity like “amide bonds” which connect the amino acids in proteins and exist as a prevalent structural motif in biomolecules. In this context, we want to introduce the concept of cross-electrophile coupling by merging the photoredox and transition metal catalysis to construct carbamides from superabundant (hetero)aryl chlorides or bromides along with commercially feasible carbamoyl chlorides. However, there is barely any report on direct activation of carbamoyl chloride so far. To circumvent the challenge, we employ the intrinsic affinity of silyl radical species towards halogen atom to harness the carbamoyl radical directly from carbamoyl chlorides which is seemingly the first of its kind. The success of this protocol relies on the prior formation of ‘aryl halides to Ni-catalyst’ oxidative addition intermediate that assists in generation of the vital carbamoyl radical. The breadth of application of this technique is significantly demonstrated by the synthesis of a plethora of (hetero)aryl carbamides with diverse functionalities. As stated earlier, we outline the direct utility of this protocol by the late-stage amidation of halide containing drug molecules and pharmacophores.

Tris(o-phenylenedioxy)cyclotriphosphazene as a Promoter for the Formation of Amide Bonds Between Aromatic Acids and Amines

Synthesis ◽  
2020 ◽  
Vol 52 (21) ◽  
pp. 3253-3262
Author(s):  
Susumu Saito ◽  
Farzaneh Soleymani Movahed ◽  
Dinesh N. Sawant ◽  
Dattatraya B. Bagal
Keyword(s):  
Organic Synthesis ◽  
31P Nmr ◽  
Research Field ◽  
Structural Motif ◽  
31P Nmr Spectroscopy ◽  
Aromatic Acids ◽  
Amide Bonds ◽  
Drug Molecules ◽  
Esi Mass Spectrometry ◽  
Increasing Demand

The atom-efficient formation of amide bonds has emerged as a top-priority research field in organic synthesis, as amide bonds constitute the backbones of proteins and represent an important structural motif in drug molecules. Currently, the increasing demand for novel discoveries in this field has focused substantial attention on this challenging subject. Herein, the degradable 1,3,5-triazo-2,4,6-triphosphorine (TAP) motif is presented as a new condensation system for the dehydrative formation of amide bonds between diverse combinations of aromatic carboxylic acids and amines. The underlying reaction mechanism was investigated, and potential catalyst intermediates were characterized using 31P NMR spectroscopy and ESI mass spectrometry.

scholarly journals Organophotocatalytic selective deuterodehalogenation of aryl or alkyl chlorides

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yanjun Li ◽  
Ziqi Ye ◽  
Yu-Mei Lin ◽  
Yan Liu ◽  
Yumeng Zhang ◽  
...  
Keyword(s):  
Room Temperature ◽  
Sodium Formate ◽  
Bioactive Molecules ◽  
Co Catalyst ◽  
Aryl Chlorides ◽  
Aryl Amine ◽  
Drug Molecules ◽  
Photocatalytic System ◽  
Site Selective ◽  
Environmentally Friendly Method

AbstractDevelopment of practical deuteration reactions is highly valuable for organic synthesis, analytic chemistry and pharmaceutic chemistry. Deuterodehalogenation of organic chlorides tends to be an attractive strategy but remains a challenging task. We here develop a photocatalytic system consisting of an aryl-amine photocatalyst and a disulfide co-catalyst in the presence of sodium formate as an electron and hydrogen donor. Accordingly, many aryl chlorides, alkyl chlorides, and other halides are converted to deuterated products at room temperature in air (>90 examples, up to 99% D-incorporation). The mechanistic studies reveal that the aryl amine serves as reducing photoredox catalyst to initiate cleavage of the C-Cl bond, at the same time as energy transfer catalyst to induce homolysis of the disulfide for consequent deuterium transfer process. This economic and environmentally-friendly method can be used for site-selective D-labeling of a number of bioactive molecules and direct H/D exchange of some drug molecules.

A triazine-phosphite polymeric ligand bearing cage-like P,N-ligation sites: an efficient ligand in the nickel-catalyzed amination of aryl chlorides and phenols

RSC Advances ◽  
2016 ◽  
Vol 6 (84) ◽  
pp. 80670-80678 ◽  
Author(s):  
Farhad Panahi ◽  
Fatemeh Roozbin ◽  
Sajjad Rahimi ◽  
Mohammadesmaeil Moayyed ◽  
Aria Valaei ◽  
...  
Keyword(s):  
Transition Metal ◽  
Polymeric Material ◽  
Transition Metal Catalysis ◽  
Metal Catalysis ◽  
Aryl Chlorides ◽  
One Step ◽  
Polymeric Ligand

A reusable polymeric material containing P,N-ligation sites was prepared by a facile one-step route for application in transition-metal catalysis as a reusable P,N-ligand.

Synthesis and Functionalization of Coumarin-Pyrazole Scaffold: Recent Development, Challenges and Opportunities

2021 ◽  
Vol 18 ◽  
Author(s):  
Nitin K. Jadhav ◽  
Balkrishna R. Kale ◽  
Mohammad S. Alam ◽  
Vishwas B. Gaikwad ◽  
Virendra Prasad ◽  
...  
Keyword(s):  
Heterocyclic Compounds ◽  
Structural Motif ◽  
Pharmacological Properties ◽  
Lead Compounds ◽  
Drug Molecules ◽  
Dna And Rna ◽  
Biological Studies ◽  
Challenges And Opportunities ◽  
First Time ◽  
Made In

: Heterocycles are the main structural motif of DNA and RNA and play crucial role in various chemical reactions of metabolisms. Therefore, heterocyclic compounds show good physiological and pharmacological properties. Coumarin and pyrazole scaffold present in many commercial drug molecules and natural products. This review gives first time gives an overview of the progress made in the synthesis and functionalization of coumarin-pyrazole hybrid heterocycle. It also includes discussion on the possible reactive sites of heterocycles, functionalization and mechanistic pathways to incorporate pyrazole pharmacophore unit in synthesis. Several synthesis and biological studies revealed that combination of coumarin-pyrazole moiety is a prominent structural motif to find lead compounds in drug discovery.

scholarly journals Weak arene/nickel interaction lights on monoarylation of alcohols

2021 ◽  
Author(s):  
Zhiyan Huang ◽  
Kun Xie ◽  
Ge Meng ◽  
Jun He ◽  
Mingsong Shi ◽  
...  
Keyword(s):  
Bioactive Molecules ◽  
Hydroxyl Groups ◽  
Nickel Catalysis ◽  
Metal Catalysis ◽  
Pharmaceutical Ingredients ◽  
Aryl Bromides ◽  
Earth Abundant ◽  
Arene Ligand ◽  
Catalytic Reactivity ◽  
Aryl Ethers

Abstract Despite a growing body of work in nickel catalysis, the potential of organo-photocatalyst serving both as an arene ligand and a sensitizer remains underexplored. Here, we describe such an organo-photocatalyst to promote arylation of alcohols. Mechanistic studies suggest that the formation of sandwich complex via weak arene/nickel interaction and the resulting dexter energy transfer be responsible for this activity. This interaction provides a mechanistically alternative strategy for challenging carbon-oxygen bond assembly, where the elementary steps in transition metal catalysis previously facilitated by intermolecular photoevents replaced by more efficient intramolecular ones. With only 0.05 mol% photocatalyst loading and 8 mol% nickel bromide, a series of alcohols, diols and triols were (mono)arylated with (hetero)aryl bromides and chlorides. Importantly, many bioactive molecules and active pharmaceutical ingredients containing multiple hydroxyl groups could be efficiently monoarylated, too. This work provides a new approach to access bioactive aryl ethers, but also lights on a highly desirable direction to manipulate the catalytic reactivity of earth abundant nickel.

scholarly journals Decarboxylative sp3 C–N Coupling via Dual Copper/Photoredox Catalysis

2018 ◽  
Author(s):  
David W. C. MacMillan ◽  
Yufan Liang ◽  
Xiaheng Zhang
Keyword(s):  
Carboxylic Acids ◽  
Cross Coupling ◽  
Nickel Catalysis ◽  
Photoredox Catalysis ◽  
Drug Molecules ◽  
Rapid Construction ◽  
Coupling System ◽  
Tertiary Alkyl ◽  
Complex Drug

<p>Over the last three decades, significant progress has been made in the development of methods to construct <i>sp<sup>2</sup></i> C–N bonds using palladium, copper, or nickel catalysis. However, the incorporation of alkyl substrates to form <i>sp<sup>3</sup></i> C–N bonds remains one of the major challenges in the field of cross-coupling chemistry. Here, we demonstrate that the synergistic combination of copper catalysis and photoredox catalysis can provide a general platform to address this long-standing challenge. This novel cross-coupling system employs naturally abundant alkyl carboxylic acids and commercially available <i>N</i>-nucleophiles as coupling partners, and is applicable to a wide variety of primary, secondary, and tertiary alkyl carboxylic acids (via in situ iodonium activation). At the same time, a vast array of <i>N</i>-nucleophiles, including <i>N</i>-heterocycles, amides, sulfonamides, and anilines, can undergo C–N coupling to provide <i>N</i>-alkyl products in good to excellent efficiency at room temperature and in short order (5 minutes to 1 hour). We have also demonstrated that this C–N coupling protocol can be applied to substrates bearing multiple amines with high regioselectivity, as well as complex drug molecules, enabling the rapid construction of molecular complexity and the late stage functionalization of bioactive pharmaceuticals.</p>

Nickel-catalyzed cross-coupling of O,N-chelated diarylborinates with aryl chlorides and mesylates

2019 ◽  
Vol 43 (3) ◽  
pp. 1589-1596 ◽  
Author(s):  
Chao Ren ◽  
Jingshu Zeng ◽  
Gang Zou
Keyword(s):  
Potassium Phosphate ◽  
Cross Coupling ◽  
Nickel Catalysis ◽  
Aryl Chlorides

Practical nickel catalysis for efficient cross-coupling of O,N-chelated diarylborinates with aryl chlorides and mesylates based on air-stable yet readily activated organonickel precursor, trans-NiCl(Ph)(PPh3)2, and sterically unsymmetrical N-heterocyclic carbene in situ generated from imidazolium precursor with trihydrate potassium phosphate in toluene.

Merging Transition-Metal Catalysis with Photoredox Catalysis: An Environmentally Friendly Strategy for C–H Functionalization

Synthesis ◽  
2018 ◽  
Vol 50 (17) ◽  
pp. 3359-3378 ◽  
Author(s):  
Wen-Jun Zhou ◽  
Da-Gang Yu ◽  
Yi-Han Zhang ◽  
Yong-Yuan Gui ◽  
Liang Sun
Keyword(s):  
Transition Metal ◽  
High Selectivity ◽  
Rapid Development ◽  
Palladium Catalysis ◽  
Transition Metal Catalysis ◽  
Nickel Catalysis ◽  
Photoredox Catalysis ◽  
Reaction Conditions ◽  
Metal Catalysis ◽  
Metal Catalyzed

Transition-metal-catalyzed C–H functionalization is already a useful tool in organic synthesis, whilst the rapid development of photoredox catalysis provides new pathways for C–H functionalization with high selectivity and efficiency under mild reaction conditions. In this review, recent advances in C–H functionalization through merging transition­-metal catalysis with photoredox catalysis are discussed.1 Introduction2 Merging Nickel Catalysis with Photoredox Catalysis3 Merging Palladium Catalysis with Photoredox Catalysis4 Merging Cobalt Catalysis with Photoredox Catalysis5 Merging Photoredox Catalysis with Other Transition-Metal Catalysis­6 Conclusions

Transition-Metal-Catalyzed Hydroxylation Reaction of Aryl Halide for the Synthesis of Phenols

Synlett ◽  
2021 ◽  
Author(s):  
D. Xue ◽  
L. Yang
Keyword(s):  
Transition Metal ◽  
Aryl Halide ◽  
High Reactivity ◽  
Aryl Halides ◽  
Biologically Active ◽  
Nickel Catalysis ◽  
Aryl Chlorides ◽  
Aryl Bromides ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

AbstractPhenols are important components of pharmaceuticals, biologically active natural products, and materials. Here, we briefly discuss recent advances in catalytic hydroxylation reactions for the synthesis of phenols, with particular attention to our recent work. H2O is proved to be an efficient hydroxide reagent in converting (hetero)aryl halides into the corresponding phenols under synergistic organophotoredox and nickel catalysis. Aryl bromides as well as less reactive aryl chlorides show high reactivity in this catalytic system. This methodology can be applied to the efficient synthesis of diverse phenols and allows the hydroxylation of multifunctional pharmaceutically relevant aryl halides.1 Introduction2 Representative Methods for Transition-Metal-Catalyzed Hydroxylation of (Hetero)Aryl Halides3 Organophotoredox/Ni Dual Catalytic Hydroxylation of Aryl Halides with Water4 Summary and Outlook

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