Catalyst-Enabled Stereodivergence in Photochemical Atom Transfer Radical Addition (ATRA) of α-Iodoboronic Esters to Alkynes DOI

Qi Fan,

Jiawu Huang,

Shuang Lin

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(1), P. 299 - 307

Published: Dec. 16, 2023

The atom transfer radical addition (ATRA) to alkynes is a valuable strategy for the synthesis of allylic substituted molecules, yet it has not been applied boronic acids or their esters, which are important building blocks in organic synthesis. inherent challenge ATRA reactions control geometric selectivity. By employing different alkene isomerization techniques, namely, photochemical uphill catalysis and manganese-catalyzed halogen-abstraction/radical rebound processes, we able synthesize both isomers iodinated esters stereoselective manner. Mechanistic investigations reveal dual functionalities catalysts, acting as catalysts processes. protocols feature broad substrate scope good functional group tolerance. Importantly, iodo boryl moieties within products provide orthogonal handles further synthetic manipulations. employed here should inspire more efforts toward alkynes.

Language: Английский

Photoinduced intermolecular hydrogen atom transfer reactions in organic synthesis DOI Creative Commons
Hui Cao, Xinxin Tang,

Haidi Tang

et al.

Chem Catalysis, Journal Year: 2021, Volume and Issue: 1(3), P. 523 - 598

Published: May 24, 2021

Language: Английский

Citations

324
Photocatalytic C(sp3) radical generationviaC–H, C–C, and C–X bond cleavage DOI Creative Commons
Chia‐Yu Huang, Jianbin Li, Chao‐Jun Li

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(19), P. 5465 - 5504

Published: Jan. 1, 2022

C(sp 3 ) radicals (R˙) are of broad research interest and synthetic utility.

Language: Английский

Citations

75
Stereospecific 1,2‐Migrations of Boronate Complexes Induced by Electrophiles DOI Creative Commons
Hui Wang, Changcheng Jing, Adam Noble

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(39), P. 16859 - 16872

Published: June 27, 2020

The stereospecific 1,2-migration of boronate complexes is one the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals natural products. Typically, driven by displacement an α-leaving group, oxidation α-boryl radical, or electrophilic activation alkenyl complex. aim this article summarize recent advances rapidly expanding field electrophile-induced groups sp

Language: Английский

Citations

123
α-Borylalkyl radicals: their distinctive reactivity in modern organic synthesis DOI Open Access
N. N. Bhuvan Kumar,

Reddy Rajasekhar Reddy,

Nadim Eghbarieh

et al.

Chemical Communications, Journal Year: 2019, Volume and Issue: 56(1), P. 13 - 25

Published: Nov. 27, 2019

Organoborons are extremely important for synthetic organic chemistry; they can serve as advanced intermediates a variety of transformations. Such well-known transformation involves the loss boron moiety, creating alkyl radicals. Although these originally developed protocols radical generation remain in active use today, recent years their α-boryl carbon-centred radicals have been joined by new array strategies that offer unique reactivity to forge wider diversity organoborons often operate under mild and benign conditions. Herein, we will highlight stability α-borylalkyl remarkably advances order further utilise them C-C C-heteroatom bond formation. Their this purpose has reported over last decade an attempt guide community. Various transition-metal metal-free methods presented, more photoredox approaches discussed, mainly period 2009-2019.

Language: Английский

Citations

79
Practical and Modular Construction of C(sp3)-Rich Alkyl Boron Compounds DOI
Yangyang Yang, Jet Tsien,

Ayala Ben David

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 143(1), P. 471 - 480

Published: Dec. 21, 2020

Alkyl boronic acids and esters play an important role in the synthesis of C(sp3)-rich medicines, agrochemicals, material chemistry. This work describes a new type transition-metal-free mediated transformation to enable construction sterically hindered alkyl boron reagents practical modular manner. The broad generality functional group tolerance this method is extensively examined through variety substrates, including late-stage functionalization scaffolds relevant medicinal strategic significance approach, with as linchpins, demonstrated various downstream functionalizations compounds. two-step concurrent cross-coupling resembling formal flexible alkyl-alkyl couplings, provides general entry synthetically challenging high Fsp3-containing drug-like scaffolds.

Language: Английский

Citations

79
Radical‐Induced 1,2‐Migrations of Boron Ate Complexes DOI Creative Commons
Marvin Kischkewitz,

Florian W. Friese,

Armido Studer

et al.

Advanced Synthesis & Catalysis, Journal Year: 2019, Volume and Issue: 362(11), P. 2077 - 2087

Published: Dec. 24, 2019

Abstract 1,2‐Boron ate rearrangements represent a fundamental class of transformations to establish new C−C bonds while retaining the valuable boron moiety in product. In established ionic processes, complex is activated by an external electrophile induce 1,2‐migration from adjacent sp 3 or 2 carbon atom. Recently, two complementary radical polar crossover approaches have been explored for both classes, 1,2‐migrations and centers. This review describes general concepts this emerging research field summarizes recent developments radical‐induced carbon. magnified image

Language: Английский

Citations

78
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

55
Palladium‐Catalyzed Cascade Heck Coupling and Allylboration of Iododiboron Compounds via Diboryl Radicals DOI
Wei Yi, Xiaoyu Xie, Jiabin Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: March 6, 2024

Geminal bis(boronates) are versatile synthetic building blocks in organic chemistry. The fact that they predominantly serve as nucleophiles the previous reports, however, has restrained their potential. Herein we disclose ambiphilic reactivity of α-halogenated geminal bis(boronates), which first catalytic utilization was accomplished by merging a formal Heck cross-coupling with highly diastereoselective allylboration aldehydes or imines, providing new avenue for rapid assembly polyfunctionalized boron-containing compounds. We demonstrated this cascade reaction is efficient and compatible various functional groups, wide range heterocycles. In contrast to classical Pd(0/II) scenario, mechanistic experiments DFT calculations have provided strong evidence cycle involving Pd(I)/diboryl carbon radical intermediates.

Language: Английский

Citations

14
1,n-Bisborylalkanes via Radical Boron Migration DOI Creative Commons
Dinghai Wang, Christian Mück‐Lichtenfeld, Armido Studer

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(20), P. 9119 - 9123

Published: May 4, 2020

A systematic study of radical boron migration in diboronate complexes to form synthetically valuable 1,

Language: Английский

Citations

64
Metal-Free Radical-Mediated C(sp3)–H Heteroarylation of Alkanes DOI
Xin Shao, Xinxin Wu, Shuo Wu

et al.

Organic Letters, Journal Year: 2020, Volume and Issue: 22(19), P. 7450 - 7454

Published: Sept. 24, 2020

Herein we disclose a metal-free, N/O-centered radical-promoted Minisci reaction, in which the coupling of various heteroarenes with simple alkanes proceeds under mild conditions. The reaction conditions are neutral; no extra acid is added to preactivate N-heteroarenes reaction. N-/O-centered radicals generated directly from amide (TsNHMe) or alcohol (CF3CH2OH) visible-light irradiation. This green and eco-friendly synthetic process may find potential use medicinal chemistry.

Language: Английский

Citations

62