Synergistic Palladium/Lewis Acid‐Catalyzed Regio‐ and Stereo‐divergent Bissilylation of Alkynoates: Scope, Mechanism, and Origin of Selectivity DOI Open Access
Shuang Zhao,

Linlin Ding,

Yingman Sun

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(37)

Published: July 21, 2023

Abstract Transition metal‐catalyzed bissilylation reactions of alkynes with disilane reagents have become one the most straightforward and efficient protocols to rapidly produce structurally diverse alkenyl silicon derivatives. In these reactions, utilization unsymmetrical provided possibilities for reactivity enhancement as well synthetic merits in contrast symmetrical reagents. However, a major yet challenging objective is achieving precise control over selectivity including regioselectivity cis / trans ‐selectivity. Herein we realized first divergent alkynoates our developed air‐stable reagent 8‐(2‐substituted‐1,1,2,2‐tetramethyldisilanyl)quinoline (TMDQ) by means synergistic Pd/Lewis acid catalytic system. The system precisely dictates selectivity, resulting synthesis 1,2‐bissilyl alkenes. power alkenes serving key intermediates has been clearly demonstrated rapid construction motifs densely functionalized biologically active compounds. addition, origins switchable selectivities were elucidated experimental computational studies on reaction mechanism mainly attributed different ligand steric effects, use specific TMDQ coordination modes Lewis alkynoates.

Language: Английский

Enantio- and diastereodivergent synthesis of fused indolizines enabled by synergistic Cu/Ir catalysis DOI Creative Commons

Bing‐Ke Zhu,

Hui Xu,

Lu Xiao

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(15), P. 4134 - 4142

Published: Jan. 1, 2023

Highly selective assembly of 2,3-fused indolizines was achieved via a cascade allylation/Friedel–Crafts type reaction with Cu/Ir catalysis. This protocol furnishes stereodivergent synthesis chiral bearing three stereogenic centers excellent results.

Language: Английский

Citations

19
Catalytic C(sp)-H carboxylation with CO2 DOI
Lin Zhang, En‐Qing Gao

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 486, P. 215138 - 215138

Published: March 30, 2023

Language: Английский

Citations

14
Iron-catalyzed [3 + 2 + 1] annulation of 2-aminobenzimidazoles/3-aminopyrazoles and aromatic alkynes using N,N-dimethylaminoethanol as a one carbon synthon for the synthesis of pyrimido[1,2-a]benzimidazoles and pyrimido[1,2-b]indazoles DOI

Zemin Qin,

Ruiqin Zhang, Shenpeng Ying

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(20), P. 5624 - 5630

Published: Jan. 1, 2022

A simple and efficient method for the synthesis of pyrimido[1,2- a ]benzimidazoles b ]indazoles by three-component [3 + 2 1] annulation catalyzed FeCl 3 has been established.

Language: Английский

Citations

22
Oxygen-, Nitrogen-, and Sulfur-Containing Heterocycles: Recent Advances in De Novo Synthesis and Prospect DOI
Yongpeng Zheng, Jianxiao Li, Wanqing Wu

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(8), P. 2988 - 3025

Published: July 13, 2024

Language: Английский

Citations

4
One-pot synthesis of functionalized dihydroindolizinones from pyrrolylpropynoates and diethyl aminomalonate DOI
Maxim D. Gotsko, Ivan V. Saliy, Igor А. Ushakov

et al.

Mendeleev Communications, Journal Year: 2025, Volume and Issue: 35(1), P. 99 - 101

Published: Jan. 1, 2025

Language: Английский

Citations

0
Synergistic Palladium/Lewis Acid‐Catalyzed Regio‐ and Stereo‐divergent Bissilylation of Alkynoates: Scope, Mechanism, and Origin of Selectivity DOI
Shuang Zhao,

Linlin Ding,

Yingman Sun

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: July 21, 2023

Transition metal-catalyzed bissilylation reactions of alkynes with disilane reagents have become one the most straightforward and efficient protocols to rapidly produce structurally diverse alkenyl silicon derivatives. In these reactions, utilization unsymmetrical provided possibilities for reactivity enhancement as well synthetic merits in contrast symmetrical reagents. However, a major yet challenging objective is achieving precise control over selectivity including regioselectivity cis/trans-selectivity. Herein we realized first divergent alkynoates our developed air-stable reagent 8-(2-substituted-1,1,2,2-tetramethyldisilanyl)quinoline (TMDQ) by means synergistic Pd/Lewis acid catalytic system. The system precisely dictates selectivity, resulting synthesis 1,2-bissilyl alkenes. power alkenes serving key intermediates has been clearly demonstrated rapid construction motifs densely functionalized biologically active compounds. addition, origins switchable selectivities were elucidated experimental computational studies on reaction mechanism mainly attributed different ligand steric effects, use specific TMDQ coordination modes Lewis alkynoates.

Language: Английский

Citations

9
Synthesis of Substituted Pyrimido[1,2‐b]indazoles through (3+2+1) Cyclization of 3‐Aminoindazoles, Ketones, and N,N‐Dimethylaminoethanol as One‐Carbon Synthon DOI

Zemin Qin,

Renchao Ma,

Shenpeng Ying

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(18), P. 3263 - 3272

Published: Aug. 20, 2022

Abstract 2‐Mono‐ or 2,3‐disubstituted pyrimido[1,2‐ b ]indazoles are synthesized by a (3+2+1) three‐component cyclization of 3‐aminoindazoles, ketones, and N,N ‐dimethylaminoethanol as methine source. The reaction demonstrates good tolerance both aromatic aliphatic well various substitution patterns in air. A plausible mechanism is discussed. magnified image

Language: Английский

Citations

13
Simple pyrazoles as efficient organocatalysts for alkyne–CO2 carboxylation and one-pot construction of heterocycles DOI
Lin Zhang, Gen Li, Enhui Xing

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 2062 - 2069

Published: Jan. 1, 2024

Simple pyrazoles are highly active bifunctional organocatalysts for alkyne–CO 2 carboxylation and applicable to orthogonal tandem catalysis the one-pot construction of various heterocycles, during which unexpected acyl migration is observed.

Language: Английский

Citations

2
Phosphine-Catalyzed [3+2] Annulation of Hepta-2,3,5-trienedioates with Alkenes for the Construction of Exocyclic Olefinic Cyclopentenes DOI

Dongqiu Li,

Xiaoqian Zhang,

Wendan Han

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(14), P. 10212 - 10222

Published: July 11, 2023

Hepta-2,3,5-trienedioates 1 have been employed as substrates to explore Lewis base-catalyzed annulation reactions. This leads the discovery of a phosphine-catalyzed [3+2] with electron-deficient alkenes for construction exocyclic olefinic cyclopentenes in good yields and moderate E:Z ratios under mild conditions. The is believed proceed tandem cyclization double bond migration which ε-ester crucial both processes. reaction also showcases substrate-controlled divergent reactivity compared that previous report.

Language: Английский

Citations

6
NHC-Catalyzed [2 + 4] Annulation of Alkynyl Ester with Chalcone DOI

Fangfang Lu,

Yangxu Chen,

Song Xue

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(10), P. 6902 - 6909

Published: April 29, 2022

An NHC-catalyzed [2 + 4] cyclization of alkynyl ester with α,β-unsaturated ketone to form a pyran scaffold was developed successfully. The cheap and easily available starting materials, mild reaction conditions, moderate excellent yields, high atom economy make this strategy attractive for the syntheses highly substituted 4H-pyran derivatives.

Language: Английский

Citations

8