Discovery of a Thioxanthone–TfOH Complex as a Photoredox Catalyst for Hydrogenation of Alkenes Using p‐Xylene as both Electron and Hydrogen Sources DOI
Wenjie Kang, Bo Li, Meng Duan

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(48)

Published: Sept. 15, 2022

Hydrogenation of alkenes is one the most fundamental transformations in organic synthesis, and widely used petrochemical, pharmaceutical, food industries. Although numerous hydrogenation methods have been developed, novel types catalysis with new mechanisms hydrogen sources are still desirable. Thioxanthone (TX) energy-transfer photoreactions, but rarely photoredox processes. Herein we show that a catalytic amount TfOH as co-catalyst can tune properties TX to make it catalyst highly enhanced oxidative capability carbonylated cheap petroleum industrial product p-xylene serving source. Deuterium also be introduced by this method using D2 O D To best our knowledge, first example

Language: Английский

Highly Efficient Asymmetric Hydrogenation Catalyzed by Iridium Complexes with Tridentate Chiral Spiro Aminophosphine Ligands DOI
F. Yang, Jian‐Hua Xie, Qi‐Lin Zhou

et al.

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(3), P. 332 - 349

Published: Jan. 23, 2023

ConspectusCatalytic asymmetric hydrogenation is one of the most reliable, powerful, and environmentally benign methods for synthesis chiral molecules with high atom economy has been successfully applied in industrial production pharmaceuticals, agrochemicals, fragrances. The key to achieving highly efficient enantioselective reactions design catalysts.Our recent studies involving iridium complexes bidentate spiro aminophosphine ligands (Ir-SpiroAP) have revealed that adding another coordinating group on nitrogen form a tridentate ligand can provide catalysts markedly higher stability, enantioselectivity, efficiency. Specifically, Ir-SpiroAP bearing an added pyridine (designated Ir-SpiroPAP) exhibit activity excellent enantioselectivity wide range carbonyl compounds, including aryl ketones, β- δ-ketoesters, α,β-unsaturated ketones esters, racemic α-substituted lactones, as well electron-deficient alkenes such malonates analogues. efficiency Ir-SpiroPAP extremely high: turnover numbers reach 4.5 million, which highest value reported date molecular catalyst. Moreover, when thioether or bulky triarylphosphine afford designated SpiroSAP SpiroPNP, respectively, resulting show β-alkyl-β-ketoesters dialkyl are challenging substrates. Furthermore, containing oxazoline moiety (Ir-SpiroOAP) α-keto amides α-aryloxy lactones. above-described used pharmaceuticals other bioactive compounds.We shown combine rigid skeleton coordination stabilize catalysts. careful tailoring substituents creates environment around active metal center catalyst precisely discriminate between two faces substrate group. These factors controlling activity, We expect based iridium, transition metals, coordinated by will find more applications transformations.

Language: Английский

Citations

54
Probing the chemical ‘reactome’ with high-throughput experimentation data DOI Creative Commons
Emma King‐Smith, Simon Berritt,

Louise Bernier

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(4), P. 633 - 643

Published: Jan. 2, 2024

High-throughput experimentation (HTE) has the potential to improve our understanding of organic chemistry by systematically interrogating reactivity across diverse chemical spaces. Notable bottlenecks include few publicly available large-scale datasets and need for facile interpretation these data's hidden insights. Here we report development a high-throughput analyser, robust statistically rigorous framework, which is applicable any HTE dataset regardless size, scope or target reaction outcome, yields interpretable correlations between starting material(s), reagents outcomes. We data landscape with disclosure 39,000+ previously proprietary reactions that cover breadth chemistry, including cross-coupling chiral salt resolutions. The analyser was validated on hydrogenation datasets, showcasing elucidation significant relationships components outcomes, as well highlighting areas bias specific spaces necessitate further investigation.

Language: Английский

Citations

16
Striding the threshold of an atom era of organic synthesis by single-atom catalysis DOI Creative Commons
Wenhao Li, Jiarui Yang, Dingsheng Wang

et al.

Chem, Journal Year: 2021, Volume and Issue: 8(1), P. 119 - 140

Published: Nov. 24, 2021

Language: Английский

Citations

103
Expeditious entry into carbocyclic and heterocyclic spirooxindoles DOI

Madhu Ganesh,

Shammy Suraj

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(29), P. 5651 - 5693

Published: Jan. 1, 2022

Recent advances in the chemistry of base-, metal-, nano-metal and organo-catalyst mediated achiral chiral versions structurally diverse pharmaceutically relevant spirooxindoles are gently reviewed.

Language: Английский

Citations

48
Design and Application of Chiral Bifunctional 4-Pyrrolidinopyridines: Powerful Catalysts for Asymmetric Cycloaddition of Allylic N-Ylide DOI

Qing-Qing Luo,

Zhou Tian, Jie Tang

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(12), P. 7221 - 7232

Published: June 2, 2022

We designed bifunctional 4-pyrrolidinopyridines as powerful Lewis base catalysts. The catalyst structure features a 4-hydroxy-2-(hydroxydiphenylmethyl)pyrrolidine-1-formyl group at the pyridine's C3 site and chiral side arm C2 position of p-pyrrolidine ring. An operationally simple three-step synthetic route allows for efficient economical preparation. In comparison with other bases, exhibits excellent efficiency stereoselectivity in asymmetric (3 + 2) cycloaddition allylic N-ylide generated situ from pyrazolone-derived Morita–Baylis–Hillman carbonate, providing platform construction spiropyrazolone derivatives. reaction mechanism was thoroughly studied. Control experiments DFT calculations illustrated origin chemoselectivity stereocontrol model. H-bonding is crucial control enantioselectivity diastereoselectivity. also successfully applied reactions, such an acylative dynamic kinetic resolution to synthesize phthalidyl ester, including prodrug Talmetacin.

Language: Английский

Citations

45
Synthesis of P-stereogenic cyclicphosphinic amidesviaelectrochemically enabled cobalt-catalyzed enantioselective C–H annulation DOI
Tao Liu,

Wangqin Zhang,

Chao Xu

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(9), P. 3606 - 3614

Published: Jan. 1, 2023

We describe a cobalta-electro-catalyzed enantioselective C–H annulation of arylphosphinamides with alkynes for P-stereogenic compounds via desymmetrization and kinetic resolution processes.

Language: Английский

Citations

40
A 13-million turnover-number anionic Ir-catalyst for a selective industrial route to chiral nicotine DOI Creative Commons
Congcong Yin, Yafei Jiang, Fanping Huang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: June 22, 2023

Abstract Developing catalysts with both useful enantioselectivities and million turnover numbers (TONs) for asymmetric hydrogenation of ketones is attractive industrial production high-value bioactive chiral entities but remains a challenging. Herein , we report an ultra-efficient anionic Ir-catalyst integrated the concept multidentate ligation ketones. Biocatalysis-like efficacy up to 99% ee (enantiomeric excess), 13,425,000 TON (turnover number) 224 s −1 TOF frequency) were documented benchmark acetophenone. Up 1,000,000 achieved challenging pyridyl alkyl ketone where at most 10,000 TONs are previously reported. The showed novel preferred ONa/MH instead NNa/MH bifunctional mechanism. A selective route enantiopure nicotine has been established using this key step 500 kg batch scale, providing 40 tons scale product.

Language: Английский

Citations

34
Biomimetic asymmetric catalysis DOI Open Access
Xiao Xiao,

Kaini Xu,

Zhong‐Hua Gao

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(6), P. 1553 - 1633

Published: April 25, 2023

Language: Английский

Citations

32
Modular α-tertiary amino ester synthesis through cobalt-catalysed asymmetric aza-Barbier reaction DOI
Xianqing Wu,

Hanyu Xia,

Chenyang Gao

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 16(3), P. 398 - 407

Published: Dec. 11, 2023

Language: Английский

Citations

30
Design of C1-symmetric tridentate ligands for enantioselective dearomative [3 + 2] annulation of indoles with aminocyclopropanes DOI Creative Commons
Hai-Xia Wang, Chun Yang,

Bai-Yu Xue

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 20, 2023

Chiral polycyclic indolines are widely present in natural products and have become the focus of extensive synthetic efforts. Here, we show catalytic asymmetric dearomative [3 + 2] annulation indoles with donor-acceptor aminocyclopropanes to construct tricyclic indolines. Key success reaction is rational design C1-symmetric bifunctional tridentate imidazoline-pyrroloimidazolone pyridine ligand. Under 5 mol% Ni(OTf)2-ligand complex, diverse containing cyclopentamine moieties obtained good chemoselectivities, high diastereoselectivities, excellent enantioselectivities. An unusual cis-configuration ligand superior trans-configuration corresponding C2-symmetric nitrogen ligands reaction. Mechanistic studies by control experiments density functional theory calculations reveal a dual activation manner, where Ni(II) complex activates aminocyclopropane via coordination geminal diester, imidazolidine NH forms H-bond succinimide moiety.

Language: Английский

Citations

28