Highlighting the Rich Chemistry of the Allenone Moiety DOI Creative Commons
José M. Alonso, Pedro Almendros

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(9), P. 1332 - 1384

Published: March 14, 2023

Abstract Conjugated and non‐conjugated allenones appear as recurring motifs in organic synthesis, natural products mechanistic investigations showing unique properties applications. The ability of to build cycles has provided a direct access strained systems, medium‐sized rings, arenes, heterocycles complex polycycles. In addition, have served models catalysis. critic compilation herein presented will provide an exhaustive overview the synthetic possibilities may offer, which certainly inspire our community their search more efficient methodologies, preparation biological pharmaceutical targets, improve knowledge theoretical chemistry. Great part this review discuss aspects, catalysis innovation insights chemical transformations implying allenone motif. many examples on total synthesis pharmacologically active compounds be described. We hope that attractive chemistry, catalysis, medicinal chemistry communities. magnified image

Language: Английский

Radical NHC Catalysis DOI
Kun Liu, Max Schwenzer, Armido Studer

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(19), P. 11984 - 11999

Published: Sept. 19, 2022

Radical/radical cross-coupling reactions represent an efficient and straightforward approach for the construction of chemical bonds accordingly have drawn increasing attention over past decades. In order to achieve synthetically useful transformations, a persistent radical should be coupled with transient in accordance effect (PRE). However, known radicals outnumber by far types free radicals, which limits widespread application PRE, until today. Thus, development between has been focus, meanwhile transition-metal catalysis successfully implemented artificially prolong lifetimes, allowing their utilization formal radical/radical cross-couplings. Complementary research field recently uncovered that organocatalytically generated NHC-derived ketyl are type catalytically radicals. NHC-catalyzed transformations aldehydes carboxylic acid derivatives enabled disclosure ever-increasing number interesting reactions, different from traditional ionic processes, offering otherwise inaccessible activation modes. These discoveries opened door NHC organocatalysis manipulation reactions. Due its obvious potential synthetic organic chemistry, it is timely provide perspective on this emerging field.

Language: Английский

Citations

203
Radical transformations for allene synthesis DOI Creative Commons
Yajun Li, Hongli Bao

Chemical Science, Journal Year: 2022, Volume and Issue: 13(29), P. 8491 - 8506

Published: Jan. 1, 2022

Allenes are valuable organic molecules that feature unique physical and chemical properties. They not only often found in natural products, but also act as versatile building blocks for the access of complex molecular targets, such pharmaceuticals, functional materials. Therefore, many remarkable elegant methodologies have been established synthesis allenes. Recently, more methods radical allenes developed, clearly emphasizing associated great synthetic values. In this perspective, we will discuss recent important advances

Language: Английский

Citations

79
NHC and visible light-mediated photoredox co-catalyzed 1,4-sulfonylacylation of 1,3-enynes for tetrasubstituted allenyl ketones DOI Creative Commons
Lihong V. Wang,

Ruiyang Ma,

Jiaqiong Sun

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(11), P. 3169 - 3175

Published: Jan. 1, 2022

The modulation of selectivity highly reactive carbon radical cross-coupling for the construction C-C bonds represents a challenging task in organic chemistry. N-Heterocyclic carbene (NHC) catalyzed transformations have opened new avenue acyl With this method, selective an with alkyl efficient was successfully realized. However, reaction radicals vinyl has been much less investigated. We herein describe NHC and visible light-mediated photoredox co-catalyzed 1,4-sulfonylacylation 1,3-enynes, providing structurally diversified valuable tetrasubstituted allenyl ketones. Mechanistic studies indicated that ketyl are formed from aroyl fluorides via oxidative quenching photocatalyst excited state, generated chemo-specific sulfonyl addition to finally, key provides

Language: Английский

Citations

73
Design principles of the use of alkynes in radical cascades DOI
Chaowei Hu,

Justice Mena,

Igor V. Alabugin

et al.

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 7(6), P. 405 - 423

Published: March 28, 2023

Language: Английский

Citations

50
Recent advances in combining photo- and N-heterocyclic carbene catalysis DOI Creative Commons
Xiaochen Wang,

Senhui Wu,

Rongxin Yang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(46), P. 13367 - 13383

Published: Jan. 1, 2023

This review summarizes recent advances in combining photo- and N-heterocyclic carbene catalysis, as well provides an outlook on future opportunities challenges.

Language: Английский

Citations

43
Recent advances in N-heterocyclic carbene (NHC)-catalyzed fluorination and fluoroalkylation DOI

Zefeng Jin,

Fuxiang Zhang, Xiao Xiao

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(7), P. 2112 - 2133

Published: Jan. 1, 2024

Organofluorine compounds are of high value. NHC-catalyzed fluorination and fluoroalkylation have served as powerful versatile vehicles for accessing the related organofluorines. This review focuses on recent developments in this area.

Language: Английский

Citations

25
Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis DOI Creative Commons
Feng‐Hua Zhang,

Xiaochong Guo,

Xianrong Zeng

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Aug. 26, 2022

Abstract The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. stereoselective 1,4-functionalization 1,3-enynes, prevalent synthon synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendous efforts have been focused on ionic reaction pathway. radical-involved asymmetric 1,3-enynes remains prominent challenge. Herein, we describe three-component 1,4-dialkylation via dual chromium to provide allenols. This method features readily available starting materials, broad substrate scope, good functional group compatibility, high regioselectivity, simultaneous control axial central chiralities. Mechanistic studies suggest that this proceeds through redox-neutral

Language: Английский

Citations

67
Electrochemically promoted N-heterocyclic carbene polymer-catalyzed cycloaddition of aldehyde with isocyanide acetate DOI

Chuhong Ou,

Ying‐Ming Pan, Haitao Tang

et al.

Science China Chemistry, Journal Year: 2022, Volume and Issue: 65(10), P. 1873 - 1878

Published: Sept. 15, 2022

Language: Английский

Citations

55
N-Heterocyclic-Carbene-Catalyzed C–H Acylation via Radical Relay DOI
Yunquan Man, Shiwen Liu, Bo Xu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(3), P. 944 - 948

Published: Jan. 20, 2022

A method of N-fluorocarboxamide-directed N-heterocyclic-carbene (NHC)-catalyzed benzylic C-H acylation with aldehydes via the hydrogen atom transfer strategy is disclosed. This transformation involves a sequence single-electron transfer, 1,5-hydrogen and radical cross-coupling steps. offers facile access to various highly functionalized ketones exhibits good chemical yields functional group tolerance.

Language: Английский

Citations

43
Radical Acylalkylation of 1,3-Enynes To Access Allenic Ketones via N-Heterocyclic Carbene Organocatalysis DOI
Yanqing Liu, Qing‐Zhu Li,

Xin‐Xin Kou

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(8), P. 5229 - 5241

Published: March 29, 2022

An N-heterocyclic carbene organocatalytic 1,4-difunctionalization of 1,3-enynes was developed. This strategy suitable for a broad spectrum substrates to efficiently synthesize allenic ketones bearing diverse substituents. Preliminary mechanistic studies suggest radical reaction pathway this acylalkylation process.

Language: Английский

Citations

41