Base-Promoted Formal (3 + 2) Cycloaddition of α-Halohydroxamates with Electron-Deficient Alkenyl-iminoindolines To Synthesize Spiro-indolinepyrrolidinones DOI
Xiang Zhang,

Hai-Yu Dai,

Wan-Cong Liu

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(20), P. 14619 - 14633

Published: Oct. 4, 2023

Construction of pyrrolidinyl-spiroindoles with easily available starting materials has attracted considerable attention from the synthesis community and is in great demand. Here, we describe a base-promoted formal (3 + 2) cycloaddition α-halohydroxamates alkenyl-iminoindolines. The present methodology features mild reaction conditions broad substrate scope up to 99% yield excellent diastereoselectivity. versatility this approach demonstrated through valuable synthetic transformations. Preliminary mechanistic studies shed light on mechanism process.

Language: Английский

Divergent Synthesis of Sulfur‐Containing Bridged Cyclobutanes by Lewis Acid Catalyzed Formal Cycloadditions of Pyridinium 1,4‐Zwitterionic Thiolates and Bicyclobutanes DOI
Yuanjiu Xiao, Feng Wu, Lei Tang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: May 31, 2024

Bridged cyclobutanes and sulfur heterocycles are currently under intense investigation as building blocks for pharmaceutical drug design. Two formal cycloaddition modes involving bicyclobutanes (BCBs) pyridinium 1,4-zwitterionic thiolate derivatives were described to rapidly expand the chemical space of sulfur-containing bridged cyclobutanes. By using Ni(ClO

Language: Английский

Citations

17
Photoinduced Regiodivergent and Enantioselective Cross-Coupling of Glycine Derivatives with Hydrocarbon Feedstocks DOI
Fuxing Yang,

Longxiao Chi,

Ziqi Ye

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from single set starting materials, significantly enriching their enantiomeric composition. However, design radical-mediated regiodivergent and enantioselective reactions that can accommodate wide range functional groups substrates has posed significant challenges. The obstacles primarily lie in switching regioselectivity achieving high enantiodiscrimination, especially when dealing with high-energy intermediates. To address these issues, we have developed new catalytic system integrates photoinduced hydrogen atom transfer (HAT) copper catalysis, involving fine-tuning ligands, additives, other reaction parameters. facilitates cross-couplings between N-aryl glycine ester/amide derivatives abundant hydrocarbon feedstocks through strong C(sp3)–H bond activation. This approach allows controlled stereoselective formation C(sp3)–C(sp3) C(sp3)–N bonds, yielding rich variety C- or N-alkylated esters amides commendable yields (up to 92% yield), exclusive regioselectivities (typically >20:1 rr), enantioselectivities 96% ee). Our methodology not only provides promising avenue incorporation alkyl functionalities onto specific sites biologically molecules but also offers practical while simultaneously induction within photochemical reactions.

Language: Английский

Citations

3
Pd-Catalyzed Ligand-Directed Divergent Cycloaddition of Cyclic 1-Azadienes with Oxo-1,4-dipoles DOI

Hongling Xie,

Lei Chen, Zhengyu Han

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(27), P. 5011 - 5016

Published: June 29, 2023

Ligand-directed divergent synthesis (LDS) is an important synthetic tool for the preparation of structurally diverse organic molecules without tedious steps to modify substrates. Herein, we introduce realization 3,4-, 1,2-, and 1,4-cyclization benzo[d]isothiazole-1,1-dioxide-fused azadienes (BDAs) through LDS, leading tetrahydro-2H-pyrans, oxazinanes, tetrahydro-2H-1,5-oxazocines, respectively. Using phosphinooxazoline (PHOX) ligands, have developed a [4 + 2] cycloaddition between BDAs substituted 2-alkylidenetrimethylene carbonates, providing access multi-substituted chiral tetrahydro-2H-pyrans in good yields with excellent enantio-, diastereo-, regioselectivities.

Language: Английский

Citations

23
Palladium-Catalyzed Ligand-Directed Divergent Decarboxylative Cycloadditions of Vinyloxazolidine-2,4-diones with 1,3,5-Triazinanes DOI
Zhen‐Hua Wang, Xiaohui Fu, Qun Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1589 - 1594

Published: Feb. 22, 2024

This study demonstrates a highly efficient regiodivergent ligand-controlled palladium-catalyzed cycloaddition reaction of vinyloxazolidine-2,4-diones with 1,3,5-triazinanes. In the presence diphosphine ligand, proceeds via (5+2) pathway to afford 1,3-diazepin-4-ones in excellent yields, while using monophosphine smoothly (3+2) give imidazolidin-4-ones good yields.

Language: Английский

Citations

9
Thermodynamic study of mesitylene + alkanol mixtures: Insights into molecular interactions DOI
Sweety Verma,

Suman Gahlyan,

Payal Bhagat

et al.

Journal of Molecular Liquids, Journal Year: 2023, Volume and Issue: 386, P. 122498 - 122498

Published: July 6, 2023

Language: Английский

Citations

19
Synthesis of Heptacyclic Compounds through C–H Bond Activation-Initiated Cascade Reactions DOI
Xing He,

Kangli Liu,

Shengnan Yan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(35), P. 7425 - 7430

Published: Aug. 22, 2024

Presented herein is an atom- and step-economical method enabling the precise assembly of a heptacyclic scaffold containing both azocine indoline units through cascade reactions indolin-1-yl(aryl)methanimines with diazo indanediones. The formation products involves C–H bond activation double carbene insertion followed by intramolecular condensation, retro-[2 + 2] cycloaddition, recyclization. This reaction not only provided concise straightforward strategy for synthesis otherwise difficult to obtain compounds from readily available substrates but also disclosed unprecedented mode derivatives compounds. In general, this novel synthetic protocol has advantages, such as easily obtainable substrates, structurally sophisticated products, procedure, good compatibility diverse functional groups, ready scalability. Moreover, thus obtained showed decent antiproliferative activity against three human cancer cell lines.

Language: Английский

Citations

8
Catalyst-Controlled Switchable (5 + 4)/(3 + 4) Cycloadditions for the Divergent Synthesis of Pyrazole-Fused Seven- and Nine-Membered Heterocycles DOI
Jie Wang, Ting Qi,

Shurong He

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(16), P. 10694 - 10704

Published: Aug. 1, 2023

Developing diversity-oriented synthetic approaches for medium-sized rings is of great interest, and the divergent synthesis with different ring sizes poses a challenging task. In this study, we present catalyst-controlled switchable (5 + 4)/(3 4) cycloaddition strategy seven- nine-membered heterocycles. Utilizing two 4-aminopyridine Lewis base catalysts, pyrazole-fused benzazepines or benzoxazonines can be efficiently assembled from same substrates. These products exhibit good stability without interconversion under reaction conditions elevated temperatures. The origin chemoselectivity was elucidated by means computational studies involving DFT calculations, distortion/interaction analysis, noncovalent interaction analysis.

Language: Английский

Citations

14
Structurally divergent enantioselective synthesis of benzofuran fused azocine derivatives and spiro-cyclopentanone benzofurans enabled by sequential catalysis DOI Creative Commons

Rupkumar Khuntia,

Sanat Kumar Mahapatra, Lisa Roy

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(39), P. 10768 - 10776

Published: Jan. 1, 2023

An important objective in organic synthesis and medicinal chemistry is the capacity to access structurally varied complex molecules rapidly affordably from easily available starting materials. Herein, a protocol for divergent of benzofuran fused azocine derivatives spiro-cyclopentanone benzofurans has been developed via chiral bifunctional urea catalyzed reaction between aurone-derived α,β-unsaturated imine ynone followed by switchable annulation reactions Lewis base catalysts (DBU PPh3) with concomitant epimerization. The skeletally diversified products were formed high yields diastereo- enantioselectivities. Computational analysis DFT accurate DLPNO-CCSD(T) employed gain deeper insights into mechanistic intricacies investigate role skeletal diversity.

Language: Английский

Citations

14
Pd-catalyzed exclusively regioselective [5 + 4] cycloaddition for the construction of 1,5-di/ox-azonanes DOI
Wenqi Liu,

Meng Zang,

Jian Zhang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(7), P. 1680 - 1685

Published: Jan. 1, 2023

An efficient approach for the exclusively regioselective construction of 1,5-di/ox-azonanes via Pd-catalyzed [5 + 4] cycloaddition has been developed.

Language: Английский

Citations

13
Palladium-Catalyzed [5 + 4] Cycloaddition of 4-Vinyl-4-Butyrolactones with N-Tosyl Azadienes: Construction of Nine-Membered Ring DOI
Lan Wang, Sen Yang, Yi Tang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(7), P. 5019 - 5028

Published: March 19, 2024

In this paper, we reported the palladium-catalyzed formal [5 + 4] cycloaddition reactions between 4-vinyl-4-butyrolactones (VBLs) and azadienes. Under mild reaction conditions, a wide range of benzofuran-fused 9-membered heterocyclic compounds had been provided in moderate to excellent yields with exclusive regioselectivities diastereoselectivities. The practical applicability synthesis was demonstrated through scale-up further transformation.

Language: Английский

Citations

5