Photocatalyzed H2-Acceptorless Dehydrogenative Borylation by Using Amine Borane DOI
Haowen Jiang,

Wan‐Lei Yu,

Dong Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8666 - 8675

Published: May 20, 2024

Catalytic dehydrogenative borylation of alkenes is arguably the most straightforward approach for synthesizing alkenyl boronates, as it eliminates need alkene or boranes prefunctionalizion. While transition-metal catalysis has conventionally been employed this transformation, competitive side reactions including hydroborylation, overborylation, and regioisomer formation always exist. In study, we present a radical catalytic borylation, which involves synergistic merger photoredox/HAT/cobalt catalysis, thereby circumventing necessity noble metals, sacrificial hydrogen acceptors, high temperatures. This method employs stable cost-effective amine borane reagents feedstocks, resulting in sole byproduct H2. methodology facilitates conversion diverse array functionalized into valuable organoboron reagents. Furthermore, late-stage complex molecules demonstrates levels site selectivity.

Language: Английский

Photocatalytic Late-Stage C–H Functionalization DOI
Peter Bellotti, Huan‐Ming Huang,

Teresa Faber

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352

Published: Jan. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Language: Английский

Citations

339
A Perspective on Late-Stage Aromatic C–H Bond Functionalization DOI Creative Commons
Li Zhang, Tobias Ritter

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(6), P. 2399 - 2414

Published: Jan. 27, 2022

Late-stage functionalization of C-H bonds (C-H LSF) can provide a straightforward approach to the efficient synthesis functionalized complex molecules. However, LSF is challenging because bond must be in presence various other functional groups. In this Perspective, we evaluate aromatic on basis four criteria─reactivity, chemoselectivity, site-selectivity, and substrate scope─and our own views current challenges as well promising strategies areas growth going forward.

Language: Английский

Citations

237
Contact-electro-catalysis for the degradation of organic pollutants using pristine dielectric powders DOI Creative Commons
Ziming Wang, Andy Berbille, Yawei Feng

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Jan. 10, 2022

Mechanochemistry has been studied for some time, but research on the reactivity of charges exchanged by contact-electrification (CE) during mechanical stimulation remains scarce. Here, we demonstrate that electrons transferred CE between pristine dielectric powders and water can be utilized to directly catalyze reactions without use conventional catalysts. Specifically, frequent at Fluorinated Ethylene Propylene (FEP) - interface induces electron-exchanges, thus forming reactive oxygen species degradation an aqueous methyl orange solution. Contact-electro-catalysis, conjunction CE, mechanochemistry catalysis, proposed as a general mechanism, which demonstrated effective various materials, such Teflon, Nylon-6,6 rubber. This original catalytic principle not only expands range also enables us envisage processes through mechano-induced contact-electrification.

Language: Английский

Citations

214
Metal-catalysed C–H bond activation and borylation DOI

Ranjana Bisht,

Chabush Haldar, Mirja Md Mahamudul Hassan

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(12), P. 5042 - 5100

Published: Jan. 1, 2022

Transition metal-catalysed direct borylation of hydrocarbons via C–H bond activation has received a remarkable level attention as popular reaction in the synthesis organoboron compounds owing to their synthetic versatility.

Language: Английский

Citations

195
Electrochemical reactor dictates site selectivity in N-heteroarene carboxylations DOI

Guo‐Quan Sun,

Peng Yu, Wen Zhang

et al.

Nature, Journal Year: 2023, Volume and Issue: 615(7950), P. 67 - 72

Published: Jan. 5, 2023

Language: Английский

Citations

186
Selective [2σ + 2σ] Cycloaddition Enabled by Boronyl Radical Catalysis: Synthesis of Highly Substituted Bicyclo[3.1.1]heptanes DOI
Tao Yu, Jinbo Yang, Zhijun Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 4304 - 4310

Published: Feb. 10, 2023

In contrast to the traditional and widely-used cycloaddition reactions involving at least a π bond component, [2σ + 2σ] radical between bicyclo[1.1.0]butanes (BCBs) cyclopropyl ketones has been developed provide modular, concise, atom-economical synthetic route substituted bicyclo[3.1.1]heptane (BCH) derivatives that are 3D bioisosteres of benzenes core skeleton number terpene natural products. The reaction was catalyzed by combination simple tetraalkoxydiboron(4) compound B2pin2 3-pentyl isonicotinate. broad substrate scope demonstrated synthesizing series new highly functionalized BCHs with up six substituents on 99% isolated yield. Computational mechanistic investigations supported pyridine-assisted boronyl catalytic cycle.

Language: Английский

Citations

128
Late-Stage C–H Functionalization of Azines DOI

Celena M. Josephitis,

Hillary M. H. Nguyen, Andrew McNally

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(12), P. 7655 - 7691

Published: May 3, 2023

Azines, such as pyridines, quinolines, pyrimidines, and pyridazines, are widespread components of pharmaceuticals. Their occurrence derives from a suite physiochemical properties that match key criteria in drug design is tunable by varying their substituents. Developments synthetic chemistry, therefore, directly impact these efforts, methods can install various groups azine C–H bonds particularly valuable. Furthermore, there growing interest late-stage functionalization (LSF) reactions focus on advanced candidate compounds often complex structures with multiple heterocycles, functional groups, reactive sites. Because factors electron-deficient nature the effects Lewis basic N atom, distinct arene counterparts, application LSF contexts difficult. However, have been many significant advances reactions, this review will describe progress, much which has occurred over past decade. It possible to categorize radical addition processes, metal-catalyzed activation transformations occurring via dearomatized intermediates. Substantial variation reaction within each category indicates both rich reactivity heterocycles creativity approaches involved.

Language: Английский

Citations

112
The interplay of polar effects in controlling the selectivity of radical reactions DOI
Alessandro Ruffoni, Rory C. Mykura, Massimo Bietti

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(9), P. 682 - 695

Published: Aug. 1, 2022

Language: Английский

Citations

100
Covalent Organic Frameworks as Porous Pigments for Photocatalytic Metal-Free C–H Borylation DOI

Ananda Basak,

Suvendu Karak, Rahul Banerjee

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(13), P. 7592 - 7599

Published: March 21, 2023

Covalent organic frameworks (COFs) are highly promising as heterogeneous photocatalysts due to their tunable structures and optoelectronic properties. Though COFs have been used photocatalysts, they mainly employed in water splitting, carbon dioxide reduction, hydrogen evolution reactions. A few examples synthesis using metal-anchored COF were reported. Herein, we report stable β-keto-enamine-based for metal-free C–B bond formation Three different availed this purpose. Their photocatalysis performances monitored 12 substrates, like quinolines, pyridines, pyrimidines. All the showcase moderate-to-high yields (up 96%) depending upon substrate's molecular functionality. High crystallinity, a large surface area, low band gap, suitable position result highest catalytic activity of TpAzo COF. The thorough mechanistic investigation further highlights crucial role light-harvesting capacity, charge separation efficiency, current density during catalysis. light absorbance capacity plays critical catalysis maximized near COF's absorption maxima. high photostability as-synthesized offers reusability several (>5) cycles.

Language: Английский

Citations

95
Borane-Catalyzed C3-Alkylation of Pyridines with Imines, Aldehydes, or Ketones as Electrophiles DOI
Zhong Liu,

Jia-Hao He,

Ming Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(11), P. 4810 - 4818

Published: March 8, 2022

Achieving C3-selective pyridine functionalization is a longstanding challenge in organic chemistry. The existing methods, including electrophilic aromatic substitution and C–H activation, often require harsh reaction conditions excess generate multiple regioisomers. Herein, we report method for borane-catalyzed tandem reactions that result exclusively alkylation of pyridines. These consist hydroboration, nucleophilic addition the resulting dihydropyridine to an imine, aldehyde, or ketone, subsequent oxidative aromatization. Because limiting reactant are mild, this constitutes practical tool late-stage structurally complex pharmaceuticals bearing moiety.

Language: Английский

Citations

77