DMAP-Catalyzed [4 + 2] Annulation of Hex-5-en-2-ynoates with Electron-Poor Alkenes DOI

Dongqiu Li,

Jiale Wu, Lulu Yang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 20, 2024

Herein, we report a DMAP-catalyzed [4 + 2] annulation reaction of hex-5-en-2-ynoates 1 with electron-poor alkenes 2, which affords exocyclic olefinic cyclohexenes 3 in good yields and excellent regio-, diastereo-, E/Z selectivities. Distinguished from previous allenoate- or alkynoate-based substrates, use the β- ε-carbons for bond formation, presenting new regiodivergent C4 synthons Lewis base-catalyzed annulations.

Language: Английский

Electrophilic hexa(methoxycarbonyl)cycloheptatrienyl anion in the synthesis of electron-deficient 5-hydroxyisoquinolones DOI

Alexander Yu. Belyy,

Alena D. Sokolova,

Rinat F. Salikov

et al.

Mendeleev Communications, Journal Year: 2025, Volume and Issue: 35(2), P. 162 - 164

Published: Jan. 1, 2025

Language: Английский

Citations

1

Enantioselective phosphine-catalyzed [6 + 1] annulations of α-allyl allenoates with 1,1-bisnucleophiles DOI Creative Commons

Jingxiong Lai,

Wei Cai, You Huang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(29), P. 11515 - 11520

Published: Jan. 1, 2024

Organocatalytic annulations between allenes and bisnucleophiles represent one of the most convenient routes to various carbocycles heterocycles. However, examples are limited formation five- six-membered rings, probably owing relatively easy handling short-chained biselectrophiles. Here we report long-chained α-allyl allenoate-derived 1,6-biselectrophiles for first time, enabling a phosphine catalyzed [6 + 1] annulation with readily available 1,1-bisnucleophilic reagents. The reaction proceeds

Language: Английский

Citations

6

Phosphine-Catalyzed Cascade Cycloaddition of Vinyl Oxiranes with Sulfonium Compounds to Step-Economically Construct Spiro-2(3H)-furanone Scaffolds DOI
Thomas P. Yang, Wei Du,

Chia‐Yu Wu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

In this work, we developed a phosphine-catalyzed cascade lactonization/[2 + 1] annulation reaction between vinyl oxiranes and sulfonium compounds for the highly diastereoselective construction of spiro-2(3H)-furanone skeletons. The cycloaddition proceeds via 2(5H)-furanone phosphonium intermediate, introducing an oxygen-containing active intermediate phosphine catalysis. These findings highlight significant potential harnessing as versatile synthons constructing spirocyclic through simultaneous multicyclic skeleton formation.

Language: Английский

Citations

0

Cyсlopentadienone and Pyrone Derivatives as Precursors of Electron-Deficient Cycloheptatrienes: Quantum Chemical Investigation and Synthesis DOI
Rinat F. Salikov, Yury V. Tomilov,

Alena D. Sokolova

et al.

Synthesis, Journal Year: 2024, Volume and Issue: 56(16), P. 2581 - 2587

Published: April 30, 2024

Abstract Unstable tetra(methoxycarbonyl)cyclopentadienone was investigated in the synthesis of electron-deficient cycloheptatrienes via [4+2]-cycloaddition/cycloelimination reaction with cyclopropenes. The use its stable dimer did not afford product although similar reactions alkynes have been reported. Quantum chemical calculation revealed that cyclopentadienone is generated from and proceeds a more complicated cycloelimination/cycloaddition/cycloelimination cascade. However, formation found favorable over dimer. Therefore, trapping upon successful to give five ester groups. methyl coumalate as four-electron component cyclopropenes containing only one group two groups product.

Language: Английский

Citations

2

Phosphine-Catalyzed [4 + 1] Annulation of β’-Acetoxy Allenoate with α-Alkylidene Succinimides: Access to Functionalized Spirosuccinimide Derivatives DOI
Chunjie Ni,

Zhanhang Liang,

Xiaojuan Xu

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(22), P. 16711 - 16720

Published: Oct. 31, 2024

A phosphine-catalyzed [4 + 1] annulation of β'-acetoxy allenoate with α-alkylidene succinimides is described. This method demonstrates the nucleophilic dialkylation and cyclization succinimides, resulting in formation functionalized spirosuccinimide derivatives. The reaction exhibits a wide substrate scope yields ranging from moderate to excellent under optimized conditions. In addition, biological evaluation indicates that cycloadduct 3u presents satisfied inhibitory activities for three human cancer cell lines (HCT116, A549, HepG2).

Language: Английский

Citations

2

Progress in Synthesis of Medium-Sized Ring Compounds Catalyzed by Organophosphine DOI

Xuling Pan,

You Huang

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(12), P. 3609 - 3609

Published: Jan. 1, 2024

Language: Английский

Citations

2

A highly diastereoselective (5+1) annulation of allenoates and pyrazolones catalyzed by CH3OK DOI

Jingxiong Lai,

You Huang

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(15), P. 2066 - 2069

Published: Jan. 1, 2024

A CH 3 OK catalyzed [5+1] annulation was developed using a newly designed allene with 1,5-biselectroephilic properties.

Language: Английский

Citations

1

Strategic 1,9-Proton-Transfer-Driven Cycloaddition: Synthesis and Stereoselective Contraction of Nine-Membered Heterocycles DOI

Sekwang Baek,

Ju Young Lee,

Min Jae Kang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 16105 - 16114

Published: Oct. 17, 2024

We introduce a phosphine-catalyzed cycloaddition involving unprecedented long-range intramolecular proton transfer, facilitating the synthesis of nine-membered heterocycles, which are privileged structures in natural products, as well potent pharmacophores. Experimental and computational studies revealed that enamide tether N-aromatic zwitterion directly enables regioselective transfer to proceed independently outer-sphere shuttling. This understanding selective has led improved efficiency regioselectivity desired 1,9-proton reaction under anhydrous conditions, thereby advancing development higher-order reactions. Further stereoselective contraction synthesized cyclic compounds using 3-aza-Cope rearrangement demonstrates synthetic versatility our approach. The findings this study not only advance general mechanism but also broaden its practical utility various chemical fields.

Language: Английский

Citations

1

Synthesis of Benzopyrone-Fused Hydrobenzo[c,d]indoles via Cascade Annulation of p-Quinamines and 3-Formylchromones DOI

Cheng Zhao,

Aiqing Zhong,

Dingxiong Xie

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(33), P. 7031 - 7036

Published: Aug. 12, 2024

A 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-catalyzed cascade annulation reaction between

Language: Английский

Citations

0

Rapid Construction of Cycloheptatriene through Organocatalyzed [4 + 3] Annulation of Coumalates DOI

Haiyan Zhang,

Han Xiao, Tong Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(36), P. 7495 - 7500

Published: Sept. 5, 2024

A protocol for the construction of cycloheptatrienes has been developed. 4-(Dimethylamino)pyridine (DMAP) was found to be an efficient catalyst promote [4 + 3] annulation between coumalates and γ-alkyl-substituted allenoate or γ-aryl-3-butynoates deliver a variety in moderate good yield with excellent chemoselectivity. The asymmetric version this also realized by using bifunctional phosphine provide chiral products 32-97% ee 29-64% yield.

Language: Английский

Citations

0