Combining Trifunctionalization of Alkynoic Acids, Arene ortho C–H Functionalization and Amination: An Approach to Unsymmetrical 2,3-Diaryl Substituted Indoles DOI
Narges Mohammadi,

Farid Mohaghegh,

Mehran Ghasemi

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(44), P. 9492 - 9497

Published: Oct. 30, 2024

Here we report a simultaneous construction of two C-C and C-N bonds in unified procedure that incorporates alkynoic acid trifunctionalization, ortho C-H functionalization, amination cascade. In an ordered process, the regioselective alkyne insertion reaction is favored over decarboxylation process. The presence carboxyl group ensures high regioselectivity carbopalladation paving way for novel method to synthesize unsymmetrically 2,3-diaryl substituted indole scaffolds with excellent regioselectivity. protocol demonstrated be suitable gram-scale synthesis.

Language: Английский

Alkyne dimerization-hydroarylation to form pentasubstituted 1,3-dienes via binuclear nickel catalysis DOI Creative Commons
Ke Chen,

Hongdan Zhu,

Shuxin Jiang

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 30, 2025

Mono-metallic catalysts dominate in homogeneous catalysis, wherein all the element steps generally occur on one metal site. Inspired from bimetallic active sites both enzymes and heterogeneous catalysts, development of binuclear catalysis can offer potential to induce novel intermediates, reactivity, selectivity. Metal-catalyzed hydroarylation alkynes leads alkyne incorporated products dimerization-hydrocarbofunctionalization is rather challenging via conventional mono-metallic intermediates. Herein, a highly selective internal achieved dinickel leading formation synthetically pentasubstituted 1,3-dienes. Mechanistic studies suggest that each Ni site promote distinct elementary two generate di-vinyl di-Ni intermediate. Such mode "binuclear convergent catalysis" fundamentally different traditional may provide new understanding synergistic effects at atomic molecular level. Here authors report

Language: Английский

Citations

0

Organic Peroxides in Transition-Metal-Free Cyclization and Coupling Reactions (C–C) via Oxidative Transformation DOI Creative Commons
Amin Rezaeifard, Fatemeh Doraghi, Fatemeh Akbari

et al.

ACS Omega, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Transition-metal-free transformations are recognized as green and sustainable methods for constructing carbon-carbon bonds in organic synthesis. This review describes the application of six peroxides, including tert-butyl hydroperoxide (TBHP), di-tert-butyl peroxide (DTBP), peroxybenzoate (TBPB), benzoyl (BPO), dialauroyl (DLP), diguyl (DCP), C-C bond construction, highlighting selected examples mechanisms challenging transformations. Each section concludes with a detailed overview suitable reagents various coupling reactions strengths weaknesses reported works. work aims to inspire further innovations transition-metal-free oxidative transformations, promoting eco-friendly chemical processes paving way new peroxide-based synthesis methods.

Language: Английский

Citations

0

The stereo-divergent functionalization of alkynes: a comprehensive review DOI Creative Commons
Ranjay Shaw,

Ashmita Singh,

Ismail Althagafi

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(16), P. 12202 - 12245

Published: Jan. 1, 2025

Stereo-divergent functionalization of alkynes for synthesizing stereochemically defined alkenes and alkanes has been compiled in this review.

Language: Английский

Citations

0

Synthesis and Transformations of O-Propargyl Analogues of Fusidic Acid DOI
Е. В. Салимова,

D. A. Golovnina,

Lyudmila V. Parfenova

et al.

Russian Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 61(3), P. 412 - 418

Published: March 1, 2025

Language: Английский

Citations

0

Nickel‐Catalyzed Sonogashira Couplings: Extending the Reaction Scope to Aryl Bromides and Chlorides DOI
Elena Braconi, Edouard Godineau, Tomáš Šmejkal

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1551 - 1558

Published: Feb. 7, 2024

Abstract The alkyne motif is present in several naturally occurring molecules and specialty chemicals. Sonogashira reaction recognized as one of the most exploited methods for synthesis substituted alkynes. While palladium catalysts have been traditionally employed, recent efforts directed towards developing alternatives based on Earth‐abundant metals such nickel. However, nickel‐catalyzed couplings still important substrate limitations. more reactive aryl iodides well documented, coupling challenging yet cost‐effective bromides chlorides lags significantly behind. Herein, we a method chlorides, whose discovery was accelerated thanks to high‐throughput experimentation. Fine‐tuning bipyridine ligand essential activate chemoselectively C( sp 2 )−Br or )−Cl bonds. A wide range functionally diverse alkynes, including examples active ingredients their intermediates, were accessed single step with yields up 98%. developed methodology expected be widely adopted by academia industry, marking forward field base metal catalysis.

Language: Английский

Citations

3

Enantioselective Divergent Syntheses of Diterpenoid Pyrones DOI

Yunpeng Ji,

Yaqian Liu,

Weiqiang Guan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9395 - 9403

Published: March 18, 2024

Capitalizing a synergy between late-stage C(sp3)–H alkynylation and series of transition metal-catalyzed alkyne functionalization reactions, we reported herein enantioselective divergent synthesis 10 diterpenoid pyrones within 14–16 steps starting from chiral pool enoxolone, including the first higginsianins A, B, D, E, metarhizin C. Our also highlights an unprecedented biomimetic oxidative rearrangement α-pyrone into 3(2H)-furanone, as well applications Echavarren reaction Toste counterion-mediated Au-catalyzed intramolecular allene hydroalkoxylation in natural product synthesis.

Language: Английский

Citations

3

Transition metal catalysed cascade C–C and C–O bond forming events of alkynes DOI

Padmanava Barik,

Subhra Sriharsa Behera,

Laxmi Kanta Nayak

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(25), P. 5052 - 5086

Published: Jan. 1, 2024

1,2/1,1-Difunctionalization of alkynes (cascade C–C and C–O bond formations) serves as one the reliable methods for synthesis numerous chemical architectures.

Language: Английский

Citations

3

Merging σ‐Bond Metathesis with Polymerization Catalysis: Insights into Rare‐Earth Metal Complexes, End‐Group Functionalization, and Application Prospects DOI Creative Commons
Friederike Adams

Macromolecular Rapid Communications, Journal Year: 2024, Volume and Issue: 45(15)

Published: June 3, 2024

Abstract Polymers with well‐defined structures, synthesized through metal‐catalyzed processes, and having end groups exhibiting different polarity reactivity than the backbone, are gaining considerable attention in both scientific industrial communities. These polymers show potential applications as fundamental building blocks additives creation of innovative functional materials. Investigations directed toward identifying most optimal uncomplicated synthetic approach by employing a combination living coordination polymerization mediated rare‐earth metal complexes C–H bond activation reaction σ‐bond metathesis. This directly yields catalysts diverse from single precursor, enabling production terminal‐functionalized without need for sequential reactions, such termination reactions. The utilization this methodology allows precise control over end‐group functionalities, providing versatile to tailor properties resulting polymers. perspective discusses principles, challenges, advancements associated strategy, highlighting its significance advancing interface metalorganic chemistry, polymer materials science.

Language: Английский

Citations

3

Metalla-Electrocatalyzed Alkyne Annulations via C–H Activations for Sustainable Heterocycle Syntheses DOI Creative Commons
Preeti Kushwaha, Anjali Saxena, Tristan von Münchow

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Herein, an overview of the evolution electrochemical C–H annulations with alkynes for construction heterocycles is provided, a topical focus on underlying mechanism manifolds.

Language: Английский

Citations

3

Atroposelective Construction of Tetrasubstituted Axially Chiral Alkene Frameworks DOI
Ying He, Jiayu Zou,

Wan-Yi Xu

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 56(12), P. 1862 - 1872

Published: Dec. 14, 2023

Abstract The construction of axially chiral alkene frameworks is currently one hottest topics in the field organic synthetic chemistry. Compared to traditional molecules, such as biaryls, heterobiaryls, and anilides, synthesis alkenes far more challenging, especially for acyclic tetrasubstituted analogues. In this review, we summarized development strategies analogues, including asymmetric difunctionalization, C–H functionalization, cross-coupling, (dynamic) kinetic resolution, allylic substitution-isomerization. 1 Introduction 2 Synthesis Cyclic Tetrasubstituted Axially Chiral Alkenes 3 Acyclic 4 Summary Outlook

Language: Английский

Citations

8