Manganese catalyzed acceptorless dehydrogenative borylation of styrenes DOI Creative Commons
Kuhali Das, Abhishek Kundu, Debashis Adhikari

et al.

Research Square (Research Square), Journal Year: 2022, Volume and Issue: unknown

Published: Sept. 19, 2022

Abstract Alkenyl boronate esters are important synthons for various pharmaceuticals, agrochemicals, natural products, and material science. Direct alkene sp2 C-H bond borylation is highly valued its synthesis. However, the drawbacks associated with chemo-, regio- stereoselectivity, using late transition metal catalysts, need sacrificial hydrogen scavengers impeded practicability sustainability. Herein, we utilized a 3d complex as catalyst synthesizing alkenyl via dehydrogenative coupling of styrenes pinacolborane. Hydrogen gas produced sole byproduct without needing an acceptor, making process green atom-economical. The methodology depicted excellent selectivity towards over direct hydroboration. Borylation aromatic alkenes aliphatic ones was also noticed. Derivatives products bioactive molecules underwent successful diversification. product could be employed several drugs potential anticancer agents. Thorough experimental high-level computational studies were performed to delineate reaction pathway. hemilability metal-ligand bifunctionality ligand backbone found crucial catalytic turnover.

Language: Английский

Synthesis of Borylated Carbocycles by [2 + 2]-Cycloadditions and Photo-Ene Reactions DOI
Jarett M. Posz,

Neetu Sharma,

Paige A. Royalty

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 10142 - 10149

Published: March 27, 2024

Saturated bicyclic compounds make up a valuable class of building blocks in the development agrochemicals and pharmaceuticals. Here, we present synthesis borylated bicyclo[2.1.1]hexanes via crossed [2 + 2]-cycloaddition. Due to presence C–B bond, variety structures can be easily prepared that are not accessible by other methods. Moreover, rare photo-ene reaction is also disclosed, allowing for diastereoselective trisubstituted cyclopentanes.

Language: Английский

Citations

28
The Impact of Boron Hybridisation on Photocatalytic Processes DOI Creative Commons

Alessandro Marotta,

Callum E. Adams,

John J. Molloy

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: June 24, 2022

Recently the fruitful merger of organoboron chemistry and photocatalysis has come to forefront organic synthesis, resulting in development new technologies access complex (non)borylated frameworks. Central success this combination is control boron hybridisation. Contingent on photoactivation mode, as its neutral planar form or tetrahedral boronate can be used regulate reactivity. This Minireview highlights current state art photocatalytic processes utilising compounds, paying particular attention role hybridisation for target transformation.

Language: Английский

Citations

56
Boronic Ester Enabled [2 + 2]-Cycloadditions by Temporary Coordination: Synthesis of Artochamin J and Piperarborenine B DOI
Yanyao Liu, Dongshun Ni, M. Kevin Brown

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(41), P. 18790 - 18796

Published: Oct. 6, 2022

A strategy for the photosensitized cycloaddition of alkenylboronates and allylic alcohols by a temporary coordination is presented. The process allows synthesis diverse range cyclobutylboronates. Key to development these reactions alcohol Bpin unit. This not only reaction proceed in an intramolecular manner but also high levels stereo regiocontrol. key aspect studies utility cycloadducts complex natural products artochamin J piperarborenine B.

Language: Английский

Citations

32
Metal–Organic Bichromophore Lowers the Upconversion Excitation Power Threshold and Promotes UV Photoreactions DOI Creative Commons
Han Li, Cui Wang, Felix Glaser

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 11402 - 11414

Published: May 15, 2023

Sensitized triplet–triplet annihilation upconversion is a promising strategy to use visible light for chemical reactions requiring the energy input of UV photons. This avoids unsafe ultraviolet sources and can mitigate photo-damage provide access reactions, which filter effects hamper direct excitation. Here, we report new approach make blue-to-UV more amenable photochemical applications. The tethering naphthalene unit cyclometalated iridium(III) complex yields bichromophore with high triplet (2.68 eV) naphthalene-based reservoir featuring lifetime 72.1 μs, roughly factor 20 longer than photoactive excited state parent complex. In combination three different annihilators, consistently lower thresholds crossover from quadratic into linear excitation power dependence regime were observed compared system composed 2,5-diphenyloxazole annihilator sufficiently robust under long-term blue irradiation continuously high-energy singlet-excited that drive normally light. Both photoredox transfer catalyses feasible using this concept, including reductive N–O bond cleavage Weinreb amides, C–C coupling reaction based on aryl debromination, two Paternò–Büchi [2 + 2] cycloaddition reactions. Our work seems relevant in context developing strategies driving energetically demanding photochemistry low-energy

Language: Английский

Citations

21
Dearomative Construction of 2D/3D Frameworks from Quinolines via Nucleophilic Addition/Borate‐Mediated Photocycloaddition DOI

Asuha Shimose,

Shiho Ishigaki,

Yu Sato

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: May 28, 2024

Dearomative construction of multiply-fused 2D/3D frameworks, composed aromatic two-dimensional (2D) rings and saturated three-dimensional (3D) rings, from readily available quinolines has greatly contributed to drug discovery. However, dearomative cycloadditions in the presence photocatalysts usually afford 5,6,7,8-tetrahydroquinoline (THQ)-based polycycles, access 1,2,3,4-THQ-based structures remains limited. Herein, we present a chemo-, regio-, diastereo-, enantioselective transformation into 6-6-4-membered without any catalyst, through combination nucleophilic addition borate-mediated [2+2] photocycloaddition. Detailed mechanistic studies revealed that photoexcited borate complex, generated quinoline, organolithium, HB(pin), accelerates cycloaddition suppresses rearomatization occurs conventional Based on our analysis, also developed further photoinduced affording other types frameworks isoquinoline phenanthrene.

Language: Английский

Citations

6
Cascade cyclization of alkene-tethered acylsilanes and allylic sulfones enabled by unproductive energy transfer photocatalysis DOI Creative Commons
Yunxiao Zhang, Yizhi Zhang, Chen Ye

et al.

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

Published: Oct. 16, 2022

Abstract Developing photo-induced cascade cyclization of alkene-tethered acylsilanes is challenging, because are unstable under light irradiation. Herein, we report that the energy transfer from excited to a photocatalyst possesses lower triplet can inhibit undesired decomposition acylsilanes. With neutral Eosin Y as photocatalyst, an efficient synthesis cyclopentanol derivatives achieved with and allylic sulfones. The reaction shows broad substrate scope synthetic potential this transformation highlighted by construction which contain fused-ring or bridged-ring.

Language: Английский

Citations

26
Electrochemical assembly of isoxazoles via a four-component domino reaction DOI Creative Commons
Yuanyuan Zhao, Xinyue Li, Simon L. Homölle

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 15(3), P. 1117 - 1122

Published: Dec. 11, 2023

Multicomponent domino reactions

Language: Английский

Citations

14
The current utility and future potential of multiborylated alkanes DOI

Kane A. C. Bastick,

Dean D Roberts,

Allan J. B. Watson

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 26, 2024

Language: Английский

Citations

5
Boosting the Enantioselectivity of Conjugate Borylation of α,β‐Disubstituted Cyclobutenones with Monooxides of ChiralC2‐Symmetric Bis(phosphine) Ligands DOI
Ming Cui, Zhiyuan Zhao, Martin Oestreich

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(62)

Published: July 11, 2022

Chiral bis(phosphine) monooxides (BPMOs) derived from C

Language: Английский

Citations

20
Photosensitized [2 + 2]-Cycloadditions of Dioxaborole: Reactivity Enabled by Boron Ring Constraint Strategy DOI
Yanyao Liu, M. Kevin Brown

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(46), P. 25061 - 25067

Published: Nov. 8, 2023

A strategy to achieve photosensitized [2 + 2] cycloadditions by means of temporary ring constraint is reported. Specifically, a dioxaborole prepared that undergoes with wide variety alkenes. This overcomes some challenges the cycloaddition acyclic substrates. The products can be easily transformed into cyclobutyl diols or 1,4-dicarbonyl compounds; latter represents formal alkene vicinal diacylation. synthetic utility this method shown in synthesis valuable heterocycles and biatriosporin D.

Language: Английский

Citations

11