Asymmetric Perspective on Denitrogenative Transformation of 1,2,3‐Triazoles DOI
Pokhriyal Yamini, Akanksha Babbar, Dongari Yadagiri

et al.

Published: Nov. 22, 2024

In this chapter, we discussed the asymmetric catalysis using rhodium azavinyl carbenes derived from N -sulfonyl-1,2,3-triazoles, which are efficient and stable surrogates of diazo compounds. This approach was employed for various transformations utilizing insertion reactions, cyclopropanation cycloaddition reactions construction chiral synthetic intermediates, heterocyclic compounds like enantioselective synthesis sulfinylamidines, α-aminoketones, β/γ-amino acid derivatives, oxazolines, dihydropyrroles, pyrroloindolines, dihydro-β-carbolines. Furthermore, natural products biologically important molecules is discussed.

Language: Английский

Silver(I)/Dirhodium(II) Catalytic Platform for Asymmetric N–H Insertion Reaction of Heteroaromatics DOI
Shingo Harada,

Shumpei Hirose,

Mizuki Takamura

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 733 - 741

Published: Dec. 27, 2023

Transition-metal-catalyzed enantioselective N–H insertion reactions of carbene species offer a powerful and straightforward strategy to produce chiral nitrogen-containing compounds. Developing highly selective using indole variants can meet synthetic demand. Herein we present an asymmetric reaction into bonds the aromatic heterocycles donor/acceptor-substituted diazo compounds based on heteronuclear catalytic platform. Although previously developed catalysis comprising silver catalyst or dirhodium(II,II) paddlewheel complexes with without phosphoric acid showed modest performance, unique combination widely available Rh2(OAc)4 silver(I) phosphate dimer [(S)-TRIP-Ag]2 enabled (up 98% ee). Moreover, Ag/Rh system facilitated regioselective C–H functionalization protic indoles. Mechanistic investigation density functional theory indicated that in situ-generated Ag–Rh trimetallic enolate is protonated environment.

Language: Английский

Citations

14
Enantioselective synthesis of chiral amides by carbene insertion into amide N–H bond DOI Creative Commons

Xuan-Ge Zhang,

Zhi‐Chun Yang,

Jia‐Bin Pan

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 5, 2024

Chiral amides are important structure in many natural products and pharmaceuticals, yet their efficient synthesis from simple amide feedstock remains challenge due to its weak Lewis basicity. Herein, we describe our study of the enantioselective chiral by N-alkylation primary taking advantage an achiral rhodium squaramide co-catalyzed carbene N-H insertion reaction. This method features mild condition, rapid reaction rate (in all cases 1 min) a wide substrate scope with high yield excellent enantioselectivity. Further product transformations show synthetic potential this Mechanistic studies reveal that non-covalent interactions between catalyst intermediate play critical role enantiocontrol.

Language: Английский

Citations

6
Asymmetric Carbene Insertion into Se‐S Bonds by Synergistic Rh(II)/Guanidine Catalysis Involving Chalcogen‐Bond Assistance DOI
Xin He,

Yihua Fu,

Ruiying Xi

et al.

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

Published: Nov. 2, 2024

The efficient construction of chalcogen-atom-based chiral compounds remains a challenge, despite the importance organoselenium and organosulfur in life materials science. Chalcogen atoms can form net attractive interactions called chalcogen bonds, but it is an undeveloped tool to assist asymmetric catalysis. Herein, we report enantioselective insertion platform install stereogenic center bearing selenyl thiocyano functional groups. Our method operates by synergistic catalysis guanidine achiral dirhodium complex three-component or four-component reaction, through Se-S bond into carbene species, competing successfully with spontaneous racemic process showing high regioselectivity. As elucidated spectroscopic experiments computational studies, unique mechanism involving as well hydrogen bonding was established account for enantiocontrol. stereoselectivity holds broad array selenylthiocyanatopropanoates, which showed excellent anti-inflammatory toward IL-1β low cytotoxicity.

Language: Английский

Citations

4
CuOTf(Tol)1/2-Catalyzed O-Trifluoroethylation of Alcohols with 2,2,2-Trifluorodiazoethane DOI

Leyi Tao,

Zhi‐Yu Lei,

Lianyun Zhao

et al.

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

Published: April 21, 2025

Trifluoroethyl groups are important in medicinal chemistry since they can impart desirable properties, such as enhanced lipophilicity, metabolic stability, or binding affinity. A practical and scalable protocol has been developed for O-trifluoroethylation of alcohols with 2,2,2-trifluorodiazoethane using Cu(OTf)(Tol)1/2 catalyst under mild conditions. This novel approach demonstrated high reactivity broad substrate scope toward a diverse range alcohols, ranging from fused bridged ring systems, linear to even sugar motifs, which makes the valuable chemistry, material science, other areas where introduction trifluoroethyl would be beneficial.

Language: Английский

Citations

0
Base-promoted hydrophosphination of in situ formed aza-ortho-quinone methides for the preparation of 2-aminobenzyl phosphorus oxides DOI
Meng Gong, Fuxing Yang, Nan Huang

et al.

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: unknown, P. 155658 - 155658

Published: May 1, 2025

Language: Английский

Citations

0
High-throughput experimentation and machine learning-promoted synthesis of α-phosphoryloxy ketones via Ru-catalyzed P(O)O-H insertion reactions of sulfoxonium ylides DOI
Lin An, Jingyuan Liu,

Yougen Xu

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 10, 2024

Language: Английский

Citations

2
Diastereoselective Synthesis of 4-Hydroxy-2-quinolinones via Formal [2 + 4] Cycloaddition Reactions Using α-Diazo Pyrazoleamides as C2 Synthons DOI
Pei Li,

Maoqing Shi,

Kaixin Yang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(26), P. 5554 - 5559

Published: June 24, 2024

A rhodium-catalyzed highly stereoselective formal [2 + 4]-cycloaddition reaction of α-diazo pyrazoleamides and 2-aminophenyl ketones that produces 4-hydroxy-2-quinolinones in good yields with excellent diastereoselectivities has been developed. pyrazolium ylide species is generated from used as a C2 synthon for this cycloaddition. This protocol offers an efficient approach to variety featuring sequential quaternary centers.

Language: Английский

Citations

1
Cycloaddition and Skeleton Rearrangement of Heterocyclic Ketene Aminals (HKAs) with 1-Diazonaphthalen-2(1H)-ones for the Synthesis of Functionalized 1,2,3-Triazoles DOI

Ke-Hua Zhao,

Jin-Mei Qi,

Xing-Mei Hu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(32), P. 6866 - 6871

Published: Aug. 2, 2024

We developed a protocol for the synthesis of highly functionalized 5,6-dihydro-imidazo[1,2-

Language: Английский

Citations

1
Enantioselective Synthesis of Axially Chiral Allylic Nitriles via Nickel‐Catalyzed Desymmetric Cyanation of Biaryl Diallylic Alcohols DOI
Can Li, Jian Song, Ting Wang

et al.

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

Published: Oct. 18, 2024

Abstract Axially chiral nitriles are common motifs in organic photoelectric materials, biological compounds, and agrochemicals. Unfortunately, the limited synthetic approaches to axially have impeded their availability. Herein, we report first nickel‐catalyzed desymmetric allylic cyanation of biaryl alcohols for synthesis nitrile structures high yields with excellent enantioselectivities (up 90 % yield >99 ee ). This process enables a diverse range bearing β , γ ‐unsaturated alcohol moieties. Leveraging cyano groups as versatile functionalization handles allow further derivatization these frameworks. Density functional theory (DFT) calculations suggest that both steric electronic interactions play crucial roles determining enantioselectivity this transformation. Moreover, mild facile protocol is also applicable gram‐scale preparation nitriles.

Language: Английский

Citations

1
Ultraviolet-Light-Induced P–H Insertion of α-Halocarbenes DOI
Chenyu Liu,

Yifei Zhang,

Xiu Gu

et al.

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

Published: Nov. 29, 2024

An intriguing P–H insertion of arylhalodiazirines with H-phosphorus oxides under ultraviolet-light irradiation is described. This methodology provides an efficient and straightforward route to the construction a variety α-halophosphorus in good yields (≤95%), which represents unique example α-halocarbenes for C–P bond formation. The metal-free protocol features advantages mild reaction conditions, high atom economy, environmental friendliness.

Language: Английский

Citations

1