N-Heterocyclic Carbene-Catalyzed Atroposelective Synthesis of N–N Axially Chiral 3-Amino Quinazolinones DOI
Kuruva Balanna,

Soumen Barik,

Shilpa Barik

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8752 - 8759

Published: June 16, 2023

Although the atroposelective synthesis of biaryls and related compounds bearing axially chiral C–C bonds is well-known, C–N bond-containing relatively less explored, construction N–N has received only scant attention. Demonstrated herein N-heterocyclic carbene (NHC)-catalyzed selective amidation reaction, leading to 3-amino quinazolinones. The NHC-catalyzed reaction quinazolinones containing a free N–H moiety with α,β-unsaturated aldehydes under oxidative conditions furnished atropisomeric quinazolinone derivatives mild broad scope. Preliminary studies on experimental density functional theory-based rotational barrier determination are also presented.

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
Benzylic C−H acylation by cooperative NHC and photoredox catalysis DOI Creative Commons
Qingyuan Meng, Lena Lezius, Armido Studer

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: April 6, 2021

Methods that enable site selective acylation of sp

Language: Английский

Citations

154
Direct α-Acylation of Alkenes via N-Heterocyclic Carbene, Sulfinate, and Photoredox Cooperative Triple Catalysis DOI
Kun Liu, Armido Studer

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(13), P. 4903 - 4909

Published: March 24, 2021

N-Heterocyclic carbene (NHC) catalysis has emerged as a versatile tool in modern synthetic chemistry. Further increasing the complexity, several processes have been introduced that proceed via dual catalysis, where NHC organocatalyst operates concert with second catalytic moiety, significantly enlarging reaction scope. In biological transformations, multiple is generally used to access complex natural products. Guided by strategy, triple studied recently, three different modes are merged single process. this Communication, direct α-C–H acylation of various alkenes aroyl fluorides using NHC, sulfinate, and photoredox cooperative reported. The method allows preparation α-substituted vinyl ketones moderate high yields excellent functional group tolerance. Mechanistic studies reveal these cascades through sequential radical addition/coupling/elimination contrast known operate two sets interwoven cycles, process, all cycles interwoven.

Language: Английский

Citations

151
Aryl radical-mediated N-heterocyclic carbene catalysis DOI Creative Commons

Yuki Matsuki,

Nagisa Ohnishi,

Yuki Kakeno

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: June 22, 2021

Abstract There have been significant advancements in radical reactions using organocatalysts modern organic synthesis. Recently, NHC-catalyzed initiated by single electron transfer processes actively studied. However, the reported examples limited to catalysis mediated alkyl radicals. In this article, NHC organocatalysis aryl radicals has achieved. The enolate form of Breslow intermediate derived from an aldehyde and thiazolium-type presence a base undergoes iodide, providing radical. catalytically generated could be exploited as arylating reagent for relay-type arylacylation styrenes hydrogen atom abstraction α-amino C(sp 3 )–H acylation secondary amides.

Language: Английский

Citations

143
Carbene and photocatalyst-catalyzed decarboxylative radical coupling of carboxylic acids and acyl imidazoles to form ketones DOI Creative Commons
Shi‐Chao Ren, Xing Yang, Bivas Mondal

et al.

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

Published: May 23, 2022

The carbene and photocatalyst co-catalyzed radical coupling of acyl electrophile a precursor is emerging as attractive method for ketone synthesis. However, previous reports mainly limited to prefunctionalized precursors two-component coupling. Herein, an N-heterocyclic catalyzed decarboxylative carboxylic acids imidazoles disclosed, in which the are directly used precursors. could also be generated situ by reaction acid with CDI thus furnishing formally two acids. In addition, successfully extended three-component using alkene third partner via relay process. mild conditions, operational simplicity, use reacting partners make our powerful strategy construction complex ketones from readily available starting materials, late-stage modification natural products medicines.

Language: Английский

Citations

85
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
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
Radical Reactions with N-Heterocyclic Carbene (NHC)-Derived Acyl Azoliums for Access to Multifunctionalized Ketones DOI

Hui Cai,

Xiaoqun Yang,

Shi‐Chao Ren

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8270 - 8293

Published: May 13, 2024

As one of the most important key intermediates, NHC-bound acylazolium-based ionic transformations have been intensively explored in past two decades. With expeditious development NHC-catalyzed radical recent years, acylazolium chemistry has reached another level, with number relevant publications increasing significantly. However, a summary focused on acylations NHC-derived acyl azoliums classified according to mechanistic difference not reported. Such detailed classification and deep analysis provide opportunities for better understanding history trend this field. In review, reactions N-heterocyclic carbene (NHC)-derived are systematically introduced. The achievements challenges within area also summarized discussed at end.

Language: Английский

Citations

23
Remote site-selective arene C–H functionalization enabled by N-heterocyclic carbene organocatalysis DOI
Qing‐Zhu Li,

Wen‐Lin Zou,

Zhaoyuan Yu

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(8), P. 900 - 911

Published: July 11, 2024

Language: Английский

Citations

17