Advances in Asymmetric Amino Acid Synthesis Enabled by Radical Chemistry DOI
Vladimir A. Larionov,

Nadezhda V. Stoletova,

Victor I. Maleev

et al.

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(20), P. 4325 - 4367

Published: Sept. 2, 2020

Abstract Chiral amino acids (AAs), being the main “building” blocks of living organisms, are also an important class organic compounds which broadly applied in synthetic chemistry, biochemistry, catalysis and designing new drugs. According to industrial‐commodity market, chiral non‐proteinogenic AAs containing various functional groups come fore. To date, radical cross‐coupling reactions becoming option as attractive powerful tool for AA syntheses. Owing mild reaction conditions high functional‐group tolerance, chemistry represents ideal strategy synthesis challenging complex AAs. Moreover, allows introducing residue into drug scaffolds natural compounds. In present review, we wish summarize discuss all reported date methods asymmetric using by presenting a comprehensive account literature this field going back 1990. We especially emphasize on approach and, exclusively, stereoselective α‐, β‐, γ‐AAs derivatives employing different type initiators starting from AIBN organostannes ending with photoredox catalysis. Furthermore, mechanism will be discussed. magnified image

Language: Английский

Photoexcited nitroarenes for the oxidative cleavage of alkenes DOI
Alessandro Ruffoni, Charlotte Hampton, Marco Simonetti

et al.

Nature, Journal Year: 2022, Volume and Issue: 610(7930), P. 81 - 86

Published: Aug. 23, 2022

Language: Английский

Citations

140
Photoinduced Oxygen Transfer Using Nitroarenes for the Anaerobic Cleavage of Alkenes DOI
Dan E. Wise, Emma Gogarnoiu,

Alana Duke

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(34), P. 15437 - 15442

Published: Aug. 5, 2022

Herein we report the anaerobic cleavage of alkenes into carbonyl compounds using nitroarenes as oxygen transfer reagents under visible light. This approach serves a safe and practical alternative to mainstream oxidative protocols, such ozonolysis Lemieux–Johnson reaction. A wide range possessing oxidatively sensitive functionalities underwent generate derivatives with high efficiency regioselectivity. Mechanistic studies support that transformation occurs via direct photoexcitation nitroarene followed by nonstereospecific radical cycloaddition event alkenes. leads 1,3,2- 1,4,2-dioxazolidine intermediates fragment give products. combination clock experiments in situ photoNMR spectroscopy revealed identities key species putative aryl dioxazolidine intermediates, respectively.

Language: Английский

Citations

93
Construction of Crystalline Nitrone-Linked Covalent Organic Frameworks Via Kröhnke Oxidation DOI
Fangyuan Kang, Xin Wang, Cailing Chen

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15465 - 15472

Published: July 7, 2023

Developing diverse synthetic routes to prepare various crystalline covalent organic frameworks (COFs) and enrich the family of COFs is very important highly desirable. In this research, we demonstrate that Kröhnke oxidation (originally developed carbonyl compounds) can be employed as an efficient method construct two nitrone-linked (CityU-1 CityU-2) through ingenious design polynitroso-containing precursors well exquisite control polymerization conditions. The formation structure nitrone-based linkage units have been confirmed a mode reaction. as-obtained characterized by Fourier transform infrared X-ray photoelectron spectroscopy, powder diffraction patterns, scanning electron microscopy. Notably, CityU-1 exhibits BET specific surface area 497.9 m2g-1 with I2 capture capacity 3.0 g g-1 at 75 °C. Our research would provide more chances for applications.

Language: Английский

Citations

86
Eu(OTf)3‐Catalyzed Formal Dipolar [4π+2σ] Cycloaddition of Bicyclo‐[1.1.0]butanes with Nitrones: Access to Polysubstituted 2‐Oxa‐3‐azabicyclo[3.1.1]heptanes DOI
Jian Zhang,

Jia‐Yi Su,

Hanliang Zheng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Jan. 30, 2024

Abstract Herein, we have synthesized multifunctionalized 2‐oxa‐3‐azabicyclo[3.1.1]heptanes, which are considered potential bioisosteres for meta ‐substituted arenes, through Eu(OTf) 3 ‐catalyzed formal dipolar [4π+2σ] cycloaddition of bicyclo[1.1.0]butanes with nitrones. This methodology represents the initial instance fabricating bicyclo[3.1.1]heptanes adorned multiple heteroatoms. The protocol exhibits both mild reaction conditions and a good tolerance various functional groups. Computational density theory calculations support that mechanism likely involves nucleophilic addition nitrones to bicyclo[1.1.0]butanes, succeeded by an intramolecular cyclization. synthetic utility this novel has been demonstrated in concise synthesis analogue Rupatadine.

Language: Английский

Citations

47
Copper-Catalyzed Enantioselective [4π + 2σ] Cycloaddition of Bicyclobutanes with Nitrones DOI

Xuan-Ge Zhang,

Zi-Yang Zhou,

Jiaxin Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 25, 2024

The selective construction of bridged bicyclic scaffolds has garnered increasing attention because their extensive use as saturated bioisosteres arene in pharmaceutical industry. However, sharp contrast to racemic counterparts, assembling chiral structures an enantioselective and regioselective manner remains challenging. Herein, we describe our protocol for constructing 2-oxa-3-azabicyclo[3.1.1]heptanes (BCHeps) by [4π + 2σ] cycloadditions bicyclo[1.1.0]butanes (BCBs) nitrones taking advantage a copper(II) complex Lewis acid catalyst. This method features mild conditions, good functional group tolerance, high yield (up 99%), excellent enantioselectivity 99% ee). Density theory (DFT) calculation elucidates the origin reaction's mechanism BCB activation Cu(II) complex.

Language: Английский

Citations

18
Regio‐ and Enantioselective (3+3) Cycloaddition of Nitrones with 2‐Indolylmethanols Enabled by Cooperative Organocatalysis DOI

Tian‐Zhen Li,

Si‐Jia Liu,

Yu‐Wen Sun

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(5), P. 2355 - 2363

Published: Oct. 22, 2020

Abstract The regio‐ and enantioselective (3+3) cycloaddition of nitrones with 2‐indolylmethanols was accomplished by the cooperative catalysis hexafluoroisopropanol (HFIP) chiral phosphoric acid (CPA). Using this approach, a series indole‐fused six‐membered heterocycles were synthesized in high yields (up to 98 %), excellent enantioselectivities 96 % ee ) exclusive regiospecificity. This approach enabled not only first organocatalytic asymmetric but also C3‐nucleophilic 2‐indolylmethanols. More importantly, theoretical calculations elucidated role cocatalyst HFIP helping CPA control reactivity enantioselectivity reaction, demonstrating new mode catalysis.

Language: Английский

Citations

104
Copper-Catalyzed Asymmetric Reaction of Alkenyl Diynes with Styrenes by Formal [3 + 2] Cycloaddition via Cu-Containing All-Carbon 1,3-Dipoles: Access to Chiral Pyrrole-Fused Bridged [2.2.1] Skeletons DOI

Feng‐Lin Hong,

Yang‐Bo Chen,

Si‐Han Ye

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(16), P. 7618 - 7626

Published: April 2, 2020

The generation of metal-containing 1,3-dipoles from metal carbenes represents a significant advance in 1,3-dipolar cycloaddition reactions. However, these transformations have so far been limited to reactions based on diazo compounds or triazoles as precursors. Herein, we disclose copper-catalyzed enantioselective reaction alkenyl N-propargyl ynamides with styrene derivatives by formal [3 + 2] via Cu-containing all-carbon 1,3-dipoles, which constitutes novel way for the carbenes. This protocol allows practical and atom-economical synthesis valuable chiral pyrrole-fused bridged [2.2.1] skeletons moderate good yields (up 90% yield) excellent diastereoselectivities (dr > 50/1) generally enantioselectivities >99% ee).

Language: Английский

Citations

99
Bioorthogonal Reactions Utilizing Nitrones as Versatile Dipoles in Cycloaddition Reactions DOI

Didier A. Bilodeau,

Kaitlyn D. Margison,

Mariam Serhan

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(12), P. 6699 - 6717

Published: Jan. 19, 2021

Bioorthogonal chemical reactions have emerged as convenient and rapid methods for incorporating unnatural functionality into living systems. Different prototype been optimized use in biological settings. Optimization of 3 + 2 dipolar cycloadditions involving nitrones has resulted highly efficient reaction conditions bioorthogonal chemistry. Through substitution at the nitrone carbon or nitrogen atom, stereoelectronic tuning reactivity dipole assisted optimizing reactivity. Nitrones shown to react rapidly with cyclooctynes bimolecular rate constants approaching k2 = 102 M–1 s–1, which are among fastest reported (McKay et al. Org. Biomol. Chem. 2012, 10, 3066–3070). also trans-cyclooctenes (TCO) strain-promoted TCO-nitrone reactions. Copper catalyzed alkynes applications biology. This review provides a comprehensive accounting different that developed using versatile reactants, some recent examples probing

Language: Английский

Citations

94
C–H Bond Functionalization of Amines: A Graphical Overview of Diverse Methods DOI Creative Commons

Subhradeep Dutta,

Bowen Li,

Dillon R. L. Rickertsen

et al.

SynOpen, Journal Year: 2021, Volume and Issue: 05(03), P. 173 - 228

Published: July 1, 2021

This Graphical Review provides a concise overview of the manifold and mechanistically diverse methods that enable functionalization sp

Language: Английский

Citations

65
Oxidation-Induced “One-Pot” Click Chemistry DOI Creative Commons
Bauke Albada, Jordi F. Keijzer, Han Zuilhof

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(12), P. 7032 - 7058

Published: March 4, 2021

Click chemistry has been established rapidly as one of the most valuable methods for chemical transformation complex molecules. Due to rapid rates, clean conversions products, and compatibility reagents reaction conditions even in settings, it found applications many molecule-oriented disciplines. From vast landscape click reactions, approaches have emerged past decade centered around oxidative processes generate situ highly reactive synthons from dormant functionalities. These led some fastest reactions know date. Here, we review various that can be used such oxidation-induced "one-pot" small molecules, materials, biomolecules. A comprehensive overview is provided oxidation induce a reaction, are orthogonal other so sequential "click-oxidation-click" derivatization molecules performed pot. Our relevant literature shows this strategy emerging powerful approach preparation high-performance materials generation As such, expect will widen scope substantially forthcoming years.

Language: Английский

Citations

60