Stereoselective P(III)‐Glycosylation for the Preparation of Phosphinated Sugars DOI
Xuan Zhang,

Xian‐Xiao Chen,

Zi‐Han Li

et al.

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

Published: Dec. 6, 2024

Abstract Most of the reported work focus on development O ‐, N C ‐ and S ‐glycosylation methods. However, no study explores P(III)‐glycosylation reaction. Herein we describe a convenient protocol to realize process. A simple β ‐phosphino ester is adopted as P(III)‐transfer reagent for this new type glycosylation via nucleophilic substitution release strategy. Diverse phosphine units are introduced anomeric center various sugars efficiently with excellent stereoselectivity. The value method showcased by prepared P(III)‐sugars novel linkers in bioactive molecule conjugation, chiral ligands metal‐catalyzed asymmetric allylic substitutions organocatalysts. Preliminary mechanistic studies corroborated designed

Language: Английский

A Hexavalent Tellurium-Based Chalcogen Bonding Catalysis Platform: High Catalytic Activity and Controlling of Selectivity DOI
Xinxin Li, Yi Liu, Wei Wang

et al.

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

Published: Jan. 13, 2025

Herein, we describe a hexavalent tellurium-based chalcogen bonding catalysis platform capable of addressing reactivity and selectivity issues. This research demonstrates that tellurium salts can serve as class highly active catalysts for the first time. The centers in these have only one exposed interaction site, thus providing favorable condition controlling reaction selectivity. advantages were demonstrated by their remarkable catalytic activity cyanidation difluorocyclopropenes through C-F bond activation, which otherwise low reactive under strong Lewis acids or inaccessible representative divalent/tetravalent donors. catalyst was further highlighted its capability to address previously unresolved problem associated with acid approach, upon using some less silyl enol ethers nucleophiles functionalization difluorocyclopropenes. generality this versatile application different systems. differentiate two similar free OH groups glycosyl acceptors achieve excellent regio- stereoselectivity synthesis disaccharides, tetravalent gave Mechanistic investigation suggests catalyst-glycosyl donor-acceptor ternary supramolecular complex is operative.

Language: Английский

Citations

1
Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy DOI Creative Commons

Wenpeng Ma,

Annika Schmidt, Carsten Strohmann

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: April 30, 2024

Abstract The utility of unconventional noncovalent interactions (NCIs) such as chalcogen bonding has lately emerged a robust platform to access synthetically difficult glycosides stereoselectively. Herein, we disclose the versatility phosphonochalcogenide (PCH) catalyst facilitate into challenging, but biologically interesting 7‐membered ring α,α’‐ C ‐disubstituted oxepane core through an α‐selective strain‐release ‐glycosylation. Methodically, this strategy represents switch from more common entropically less desired macrocyclizations thermodynamically favored ring‐expansion approach. In light general lack stereoselective methods ‐septanosides, remarkable palette silyl‐based nucleophiles can be reliably employed in our method. This include broad variety useful synthons, easily available silyl‐allyl, silyl‐enol ether, silyl‐ketene acetal, vinylogous silyl‐alkyne and silylazide reagents. Mechanistic investigations suggest that mechanistic shift towards intramolecular aglycone transposition involving pentacoordinate silicon intermediate is likely responsible steering stereoselectivity.

Language: Английский

Citations

6
Telluronium‐Catalyzed Halogenation Reactions: Chalcogen‐Bond Activation of N‐Halosuccinimides and Catalysis DOI Creative Commons

Loïc Groslambert,

Patrick Pale, Victor Mamane

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(43)

Published: May 24, 2024

The ability of triaryltelluronium salts to interact with N-halosuccinimides (NXS) through chalcogen bonding (ChB) in the solid state and solution is demonstrated herein. Cocrystals bearing two CF

Language: Английский

Citations

5
Neutral Chalcogen Bonding Enabled Photoinduced Cross‐Electrophile C—S/Se Coupling of Aryl Iodides via SRN1 Process DOI Open Access

Yongliang Tu,

Xiang Li,

Bei‐Bei Zhang

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Comprehensive Summary Cross‐coupling reactions between aryl halides and thiolates or selenolates typically require transition metals, photocatalysts, strong bases, or/and malodorous thiols/selenols, with various mechanisms proposed. This study aims to leverage a new application of neutral ChB address these challenges enable very simple photoinduced cross‐electrophile C—S/Se coupling using readily available chalcogen electrophiles. Mechanistic investigations have revealed the important role in facilitating single electron transfer processes, thereby enabling generation thiolates/selenolates from stable electrophiles α ‐aminoalkyl radicals, which possess capability abstract halogen atoms iodides. Moreover, provided support for radical nucleophilic substitution mechanism.

Language: Английский

Citations

0
Noncovalent Interactions: An emerging focal point in stereoselective catalytic carbohydrate synthesis DOI
Hao Guo, Charles C. J. Loh

Carbohydrate Research, Journal Year: 2025, Volume and Issue: unknown, P. 109458 - 109458

Published: March 1, 2025

Language: Английский

Citations

0
Both N-F oxidant and NaF determined reaction yield in the organoselenium-catalyzed oxidative ring-closing reaction of unsaturated alcohol: A theoretical study DOI
Chao-Xian Yan,

Lei-Tao Wei,

Weiqin Gao

et al.

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 567, P. 114442 - 114442

Published: Aug. 13, 2024

Language: Английский

Citations

2
Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy DOI Creative Commons

Wenpeng Ma,

Annika Schmidt, Carsten Strohmann

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(29)

Published: April 30, 2024

Abstract The utility of unconventional noncovalent interactions (NCIs) such as chalcogen bonding has lately emerged a robust platform to access synthetically difficult glycosides stereoselectively. Herein, we disclose the versatility phosphonochalcogenide (PCH) catalyst facilitate into challenging, but biologically interesting 7‐membered ring α,α’‐ C ‐disubstituted oxepane core through an α‐selective strain‐release ‐glycosylation. Methodically, this strategy represents switch from more common entropically less desired macrocyclizations thermodynamically favored ring‐expansion approach. In light general lack stereoselective methods ‐septanosides, remarkable palette silyl‐based nucleophiles can be reliably employed in our method. This include broad variety useful synthons, easily available silyl‐allyl, silyl‐enol ether, silyl‐ketene acetal, vinylogous silyl‐alkyne and silylazide reagents. Mechanistic investigations suggest that mechanistic shift towards intramolecular aglycone transposition involving pentacoordinate silicon intermediate is likely responsible steering stereoselectivity.

Language: Английский

Citations

1
A Modified Arbuzov‐Michalis Reaction for Selective Alkylation of Nucleophiles DOI
Jiaxi Wang,

Mu-Qiu Chen,

Yang Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: July 3, 2024

The alkylation of nucleophiles is among the most fundamental and well-developed transformations in chemistry. However, to achieve selective complex substrates remains a nontrivial task. We report herein general method without using strong acids, bases, or metals. In this method, readily available phosphinites/phosphites, combination with ethyl acrylate, function as effective alkylating agents. Various nucleophilic groups, including alcohols, phenols, carboxylic imides, thiols can be alkylated. This applied late-stage natural products pharmaceutical agents, achieving chemo- site-selective modification substrates. Experimental studies indicate relative reactivity nucleophile depends on its acidity steric environment. Mechanistic suggest reaction pathway resembles that Arbuzov-Michalis reaction.

Language: Английский

Citations

1
Merging radical catalysis and noncovalent stereocontrol concepts to forge native O-glycosidic linkages DOI
Hao Guo, Charles C. J. Loh

Science Bulletin, Journal Year: 2024, Volume and Issue: 69(21), P. 3308 - 3310

Published: Aug. 30, 2024

Language: Английский

Citations

1
A Modified Arbuzov‐Michalis Reaction for Selective Alkylation of Nucleophiles DOI
Jiaxi Wang,

Mu-Qiu Chen,

Yang Zhang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(41)

Published: July 3, 2024

Abstract The alkylation of nucleophiles is among the most fundamental and well‐developed transformations in chemistry. However, to achieve selective complex substrates remains a nontrivial task. We report herein general method without using strong acids, bases, or metals. In this method, readily available phosphinites/phosphites, combination with ethyl acrylate, function as effective alkylating agents. Various nucleophilic groups, including alcohols, phenols, carboxylic imides, thiols can be alkylated. This applied late‐stage natural products pharmaceutical agents, achieving chemo‐ site‐selective modification substrates. Experimental studies indicate relative reactivity nucleophile depends on its acidity steric environment. Mechanistic suggest reaction pathway resembles that Arbuzov‐Michalis reaction.

Language: Английский

Citations

0