Enantioselective Allylboration of Acetylene: A Versatile Tool for the Stereodivergent Synthesis of Natural Products DOI Creative Commons
Andrés M. Álvarez‐Constantino, Andrea Chaves‐Pouso, Martín Fañanás‐Mastral

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(34)

Published: June 11, 2024

Abstract Efficient catalytic methods that allow the use of simple and abundant chemical feedstocks for preparation synthetically versatile compounds are central to modern synthetic chemistry. Acetylene is a basic feedstock with remarkable production over one million tons per year, although it underutilized in stereoselective synthesis fine chemicals. Here we report facile multicomponent reaction allows enantio‐ diastereoselective allylboration acetylene gas. This process catalyzed by chiral copper catalyst, operates without specialized equipment or pressurization, provides skipped dienes bearing stereodefined orthogonally functionalized olefins excellent levels chemo‐, regio‐, diastereoselectivity. The combined stereochemical features orthogonal functionalization make products privileged structural scaffolds access complete set stereoisomers diene core through diastereodivergent pathways. utility method demonstrated enantioselective three bioactive natural products, namely (+)‐Nyasol, (+)‐Hinokiresinol Phorbasin C, other related relevant molecules.

Language: Английский

Construction of 3-Methyl-2-Substituted Benzo[b]furans and 3-Methyl-2-Substituted Benzo[b]thiophenes Using Solid Calcium Carbide as a Substitute for Gaseous Acetylene DOI
Zhiqiang Wang, Zhenrong Liu,

Shao Ting

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 7182 - 7186

Published: May 2, 2024

A concise method for the facile construction of 3-methyl-2-substituted benzo[b]furans and benzo[b]thiophenes using low-cost, abundant, easy-to-use solid calcium carbide instead flammable explosive gaseous acetylene as an original alkyne source, o-bromophenyl ethers or thioethers substrates through intramolecular carbanion-yne cyclization in a 5-exo-dig manner, subsequent double-bond isomerization is described. The simultaneous formation two C–C bonds realized one-step route. wide substrate scope, high yield, simple workup manipulations are also merits this method. synthetic strategy can be suitable gram scale.

Language: Английский

Citations

6
Gold‐Catalyzed Alkyne‐Amine Cascade Annulations: A Modern Strategy for Azaheterocycle Construction DOI
Alexey Yu. Dubovtsev

The Chemical Record, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Abstract Gold catalysis has experienced remarkable progress over the past two decades, particularly in transformations involving alkynes. While numerous aspects of gold‐catalyzed reactions have been extensively reviewed, specific area cascade annulations between functionalized amines and alkynes represents a distinct rapidly developing direction that warrants focused attention. This survey collects systematically analyzes these transformations, which emerged as convenient synthetic strategies to diverse nitrogen heterocycles. The relevant are classified firstly by chemical nature amine functional substituent, secondly size formed ring. field under consideration bridges several fundamental practical branches chemistry, including catalysis, organic synthesis, medicinal materials science.

Language: Английский

Citations

0
Recent progress in the catalytic transformation of acetylene DOI
Xin Yu, Shifa Zhu

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Acetylene, a traditional industrial raw material, has garnered increasing attention in modern organic synthesis over the past two decades.

Language: Английский

Citations

0
A Gold(I)–Acetylene Complex Synthesised using Single‐Crystal Reactivity DOI Creative Commons
Chloë Johnson,

Daniel J. Storm,

M. Arif Sajjad

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 3, 2024

Abstract Using single‐crystal to solid/gas reactivity the gold(I) acetylene complex [Au( L1 )(η 2 ‐HC≡CH)][BAr F 4 ] is cleanly synthesized by addition of gas single crystals )(CO)][BAr [ =tris‐2‐(4,4′‐di‐tert‐butylbiphenyl)phosphine, Ar =3,5‐(CF 3 ) C 6 H ]. This simplest gold‐alkyne has been characterized crystal X‐ray diffraction, solution and solid‐state NMR spectroscopy periodic DFT. Bonding HC≡CH with )] + comprises both σ‐donation π‐backdonation additional dispersion interactions within cavity‐shaped phosphine.

Language: Английский

Citations

2
A Gold(I)–Acetylene Complex Synthesised using Single‐Crystal Reactivity DOI Creative Commons
Chloë Johnson,

Daniel J. Storm,

M. Arif Sajjad

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(30)

Published: May 3, 2024

Abstract Using single‐crystal to solid/gas reactivity the gold(I) acetylene complex [Au( L1 )(η 2 ‐HC≡CH)][BAr F 4 ] is cleanly synthesized by addition of gas single crystals )(CO)][BAr [ =tris‐2‐(4,4′‐di‐tert‐butylbiphenyl)phosphine, Ar =3,5‐(CF 3 ) C 6 H ]. This simplest gold‐alkyne has been characterized crystal X‐ray diffraction, solution and solid‐state NMR spectroscopy periodic DFT. Bonding HC≡CH with )] + comprises both σ‐donation π‐backdonation additional dispersion interactions within cavity‐shaped phosphine.

Language: Английский

Citations

2
Modular and Diverse Synthesis of Acrylamides by Palladium‐Catalyzed Hydroaminocarbonylation of Acetylene DOI Creative Commons
Matthias Beller,

Zhusong Cao,

Qiang Wang

et al.

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

Published: July 10, 2024

The development of all kinds covalent drugs had a major impact on the improvement human health system. Covalent binding to target proteins is achieved by so-called electrophilic warheads, which are incorporated in respective drug molecule. In last decade, specifically acrylamides emerged as attractive warheads design. Herein, straightforward palladium-catalyzed hydroaminocarbonylation acetylene has been developed, allowing modular and diverse synthesis bio-active acrylamides. This general protocol features high atom efficiency, wide functional group compatibility, chemoselectivity proceeds additive free under mild reaction conditions. synthetic utility this showcased ibrutinib, osimertinib, other compound derivatives.

Language: Английский

Citations

2
Modular and Diverse Synthesis of Acrylamides by Palladium‐Catalyzed Hydroaminocarbonylation of Acetylene DOI Creative Commons
Matthias Beller,

Zhusong Cao,

Qiang Wang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(40)

Published: July 10, 2024

Abstract The development of all kinds covalent drugs had a major impact on the improvement human health system. Covalent binding to target proteins is achieved by so‐called electrophilic warheads, which are incorporated in respective drug molecule. In last decade, specifically acrylamides emerged as attractive warheads design. Herein, straightforward palladium‐catalyzed hydroaminocarbonylation acetylene has been developed, allowing modular and diverse synthesis bio‐active acrylamides. This general protocol features high atom efficiency, wide functional group compatibility, chemoselectivity proceeds additive free under mild reaction conditions. synthetic utility this showcased ibrutinib, osimertinib, other compound derivatives.

Language: Английский

Citations

2
Three-Component Gold(I)-Catalyzed Alkoxyvinylation DOI Creative Commons
L. Anders Hammarback,

Tania Medina-Gil,

Anna Sadurní

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(30), P. 6375 - 6379

Published: July 18, 2024

Acetylene has been underexploited despite being a highly valuable feedstock for chemical synthesis. We have developed the first true gold(I)-catalyzed intermolecular three-component reaction between acetylene, alkenes, and alcohols to afford β-vinyl hemiaminal scaffolds from N-vinyl amides. Unusual biscyclopropyl 3-vinyl N-heterocyclic were obtained through incorporation of second unit or tethered alkene into starting material.

Language: Английский

Citations

1
Enantioselective Allylboration of Acetylene: A Versatile Tool for the Stereodivergent Synthesis of Natural Products DOI Creative Commons
Andrés M. Álvarez‐Constantino, Andrea Chaves‐Pouso, Martín Fañanás‐Mastral

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(34)

Published: June 11, 2024

Abstract Efficient catalytic methods that allow the use of simple and abundant chemical feedstocks for preparation synthetically versatile compounds are central to modern synthetic chemistry. Acetylene is a basic feedstock with remarkable production over one million tons per year, although it underutilized in stereoselective synthesis fine chemicals. Here we report facile multicomponent reaction allows enantio‐ diastereoselective allylboration acetylene gas. This process catalyzed by chiral copper catalyst, operates without specialized equipment or pressurization, provides skipped dienes bearing stereodefined orthogonally functionalized olefins excellent levels chemo‐, regio‐, diastereoselectivity. The combined stereochemical features orthogonal functionalization make products privileged structural scaffolds access complete set stereoisomers diene core through diastereodivergent pathways. utility method demonstrated enantioselective three bioactive natural products, namely (+)‐Nyasol, (+)‐Hinokiresinol Phorbasin C, other related relevant molecules.

Language: Английский

Citations

0
Enantioselective Allylboration of Acetylene: A Versatile Tool for the Stereodivergent Synthesis of Natural Products DOI Creative Commons
Andrés M. Álvarez‐Constantino, Andrea Chaves‐Pouso, Martín Fañanás‐Mastral

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(34)

Published: June 11, 2024

Abstract Efficient catalytic methods that allow the use of simple and abundant chemical feedstocks for preparation synthetically versatile compounds are central to modern synthetic chemistry. Acetylene is a basic feedstock with remarkable production over one million tons per year, although it underutilized in stereoselective synthesis fine chemicals. Here we report facile multicomponent reaction allows enantio‐ diastereoselective allylboration acetylene gas. This process catalyzed by chiral copper catalyst, operates without specialized equipment or pressurization, provides skipped dienes bearing stereodefined orthogonally functionalized olefins excellent levels chemo‐, regio‐, diastereoselectivity. The combined stereochemical features orthogonal functionalization make products privileged structural scaffolds access complete set stereoisomers diene core through diastereodivergent pathways. utility method demonstrated enantioselective three bioactive natural products, namely (+)‐Nyasol, (+)‐Hinokiresinol Phorbasin C, other related relevant molecules.

Language: Английский

Citations

0