Palladium‐Catalyzed Silylacylation of Allenes Using Acylsilanes DOI

Tetsuya Inagaki,

Shun Sakurai,

Masahiro Yamanaka

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(21)

Published: March 9, 2022

Abstract We have developed a palladium‐catalyzed addition of C−Si bond acylsilanes across range unactivated allenes. The reaction proceeds with complete regioselectivity, in which silyl group binds to the central carbon allene, allowing for straightforward access functionalized alkenylsilane derivatives.

Language: Английский

Regioselective Difunctionalization and Annulation of Ynamide DOI
Shubham Dutta, Rajendra K. Mallick, Akhila K. Sahoo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: April 8, 2023

Abstract The use of ynamides in organic synthesis has gained significant attention due to their ability provide access complex molecular structures through transformations such as 1,2‐difunctionalization and annulation reactions. These reactions enable the formation highly functionalized N‐bearing olefins unusual heterocycles. In this minireview, we present a systematic overview regioselective difunctionalization ynamides. We discuss multi‐component reactions, radical‐triggered functionalizations across carbon–carbon multiple bonds bifunctional reagents ynamides, highlighting potential expanding substrate scope. Furthermore, insights into mechanistic breakthroughs that have been achieved recent years development these Finally, emphasize promising future prospects versatile building blocks for architectures.

Language: Английский

Citations

28
Palladium‐Catalyzed Silylacylation of Allenes Using Acylsilanes DOI

Tetsuya Inagaki,

Shun Sakurai,

Masahiro Yamanaka

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(21)

Published: March 9, 2022

We have developed a palladium-catalyzed addition of C-Si bond acylsilanes across range unactivated allenes. The reaction proceeds with complete regioselectivity, in which silyl group binds to the central carbon allene, allowing for straightforward access functionalized alkenylsilane derivatives.

Language: Английский

Citations

25
Palladium-catalyzed addition of acylsilanes across alkynes via the activation of a C–Si bond DOI Creative Commons

Tetsuya Inagaki,

Takahiro Ando,

Shun Sakurai

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(10), P. 2706 - 2712

Published: Jan. 1, 2023

Palladium-catalyzed addition of a C–Si bond in acylsilanes across the triple bonds an alkyne bearing carbonyl group at one terminal is reported.

Language: Английский

Citations

10
Nickel-catalysed Regio- and Stereoselective Hydrocyanation of Alkynoates and Its Mechanistic Insights Proposed by DFT Calculations DOI
Shigeru Arai, Koichi Nakazawa, Xiaofei Yang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(18), P. 3606 - 3610

Published: Jan. 1, 2024

This work discloses the origin of regio- and stereoselectivity hydrocyanation alkynoates.

Language: Английский

Citations

3
Silylium-Catalyzed Regio- and Stereoselective Carbosilylation of Ynamides with Allylic Trimethylsilanes DOI Creative Commons
Paz Yepes, A.L. Suarez-Sobrino, Miguel A. Rodrı́guez

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(6), P. 1020 - 1024

Published: Feb. 7, 2023

The regio- and stereoselective carbosilylation of tosylynamides with allylic trimethylsilanes takes place under mild conditions in the presence catalytic TMSNTf2 or HNTf2 to give (Z)-α-allyl-β-trimethylsilylenamides good yields. Theoretical calculations show activation C-C triple bond ynamides by trimethylsilylium ion formation a β-trimethylsilylketenimonium cation. Further transformations products demonstrate synthetic utility this reaction.

Language: Английский

Citations

8
Late-stage diversification strategy for synthesizing ynamides through copper-catalyzed diynylation and azide–alkyne cycloaddition DOI

Ryohei Kawakami,

Suguru Usui,

Norihiro Tada

et al.

Chemical Communications, Journal Year: 2022, Volume and Issue: 59(4), P. 450 - 453

Published: Dec. 9, 2022

A late-stage diversification strategy for synthesizing ynamides has been developed. This was enabled by the copper-catalyzed direct electrophilic diynylation of sulfonamides with a novel triisopropylsilyl diynyl benziodoxolone, deprotection, and chemoselective azide-alkyne cycloaddition sequence, which yields various complex molecule-derived pyrene, amino acid, nucleoside, N-acetylglucosamine as substituents.

Language: Английский

Citations

12
Heterodifunctionalization of Electron-Rich Alkynes Catalyzed by in Situ Generated Silylium Ions DOI
Xiang Su, Yong Wang, Qiang Feng

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(1), P. 421 - 426

Published: Jan. 2, 2024

Silylium ions are versatile Lewis acids in organic synthesis. While they have been well-known for the activation of σ donors, catalysis initiated by π donors remains underdeveloped, particularly alkynes. Herein, we demonstrate an example silylium-catalyzed alkyne heterodifunctionalization. The silylium ion generated situ from HNTf2 and silyl reagent serve as superior catalysts efficient silylphosphination silylcyanation electron-rich alkynes with excellent regio- stereoselectivity. compatibility this protocol strongly coordinating ligands (Ph2P CN) not only complements metal-catalyzed systems but also expands scope reactions.

Language: Английский

Citations

2
Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis DOI Creative Commons
Yuanjiu Xiao, Lei Tang, Tongtong Xu

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(21), P. 5608 - 5618

Published: Jan. 1, 2023

A boron Lewis acid catalyzes trans-carboacyloxylations of ynamides with esters to afford fully substituted acyclic enol esters/carbonates in high yields and excellent stereocontrol.

Language: Английский

Citations

6
Direct Access to 2,3-Disubstituted Amido-Indenones through Annulation of 2-Iodobenzaldehydes with Ynamides DOI

Stéphane Golling,

Pierre Hansjacob,

Nassim Bami

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(24), P. 16860 - 16866

Published: Dec. 6, 2022

In this paper we report the annulation reaction between 2-iodobenzaldehyde derivatives and various ynamides. This palladium-catalyzed leads to rare polysubstituted amino-indenones in good yields with a regioselectivity up complete. Remarkably, regiodivergent selectivity has been identified aryl alkyl or silyl ynamides, first leading mainly 2-amido-indenones second 3-amido-indenones.

Language: Английский

Citations

7
3‐Amido‐benzo[b]silines: Straightforward Modular 2‐Step Synthesis and Photophysical Properties DOI Creative Commons

Stéphane Golling,

Tianhong Yan,

Valérie Mazan

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(10), P. 2324 - 2333

Published: April 3, 2024

Abstract In this manuscript we report the synthesis of 3‐amido‐benzo[ b ]silines thanks to a 2‐step strategy involving 3‐component silylformylation ynamides followed by Friedel‐Crafts cyclization/isomerizing dehydration domino sequence. This reaction is tolerant various structural variations and has allowed us synthesize library diversely substituted silacycles with yields from 33 85%. We also studied fluorescence properties these compounds which show similarities recognized probes such as Si‐Rhodamine for example.

Language: Английский

Citations

1