Unveiling the Hidden Reactivity in the N-Heterocyclic Carbene-Catalyzed Aerobic Oxidation of Aldehydes: Unlocking Its Powerful Catalytic Performance DOI

Chenrui Fan,

Xu Zhao,

Reveendra Gopireddy

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 2, 2024

An innovative solution that overcomes the long-standing inherently low efficiency in N-heterocyclic carbene-catalyzed aerobic oxidation of aldehydes is reported. This included design and synthesis a novel polymerized catalyst utilization flow reactor. The unprecedentedly high achieved via this protocol makes it synthetically applicable. A total turnover number (TON) 26,300 was based on recycling experiments (runs). highest TON single run could be up to 2475 with frequency (TOF) 208 h–1, far superior its traditional counterpart, which typical ranges from 20 100 TOF less than 10 h–1. has been recycled over 50 times still fully active. success attributed discovery hidden reactivity, observed for first time as an autoacceleration reaction rate during kinetic investigations. research also provided concrete evidence supporting conclusion radical intermediates played crucial roles catalytic cycle by having determinative impact overall rate.

Язык: Английский

Redox-Paired Reductive Heck Reaction and Oxidative Esterification Catalyzed by Mesoionic Carbenes DOI

B. HUANG,

Zengyu Zhang, J. B. Jiao

и другие.

Organic Letters, Год журнала: 2024, Номер 26(35), С. 7419 - 7424

Опубликована: Авг. 22, 2024

Paring a reductive reaction and an oxidative in one could be immensely important achieving atom economic environmental advantages. Herein, we report simple protocol that combines two such Heck reactions esterification by using mesoionic carbenes as catalysts to synthesize multiple valuable products under mild conditions.

Язык: Английский

Процитировано

3

NHC/Pd Synergistically Catalyzed Direct Aerobic Oxidative Allylic Esterification of Aldehydes DOI
Chhanda Debnath, Shikha Gandhi

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 21, 2025

N-Heterocyclic carbene (NHC)-mediated aerobic oxidation of aldehydes has gained interest in recent years. However, its application NHC/Pd synergistic catalysis been unexplored. We have developed a strategy to synthesize allylic esters directly from and Morita-Baylis-Hillman (MBH) carbonates using (cooperative) under conditions. This transformation gives access the selective formation multifunctionalized E-alkenes by β-attack on MBH carbonates. catalytic system also allows use water as cosolvent air sole green oxidant.

Язык: Английский

Процитировано

0

Redox Active N-Heterocyclic Carbenes in Oxidative NHC Catalysis DOI Creative Commons
Sara Bacaicoa,

Simon Stenkvist,

Henrik Sundén

и другие.

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3114 - 3118

Опубликована: Март 29, 2024

An N-heterocyclic carbene (NHC) covalently linked to a quinone introduces novel avenue for internal oxidations within oxidative NHC catalysis. The deployment of this hybrid class promotes intramolecular electronic flow in the oxidation Breslow intermediate acyl azolium. use redox active as catalyst is facilitated by employing aerobic regeneration, yielding carboxylic esters with efficiencies ≤99%, while generating water sole byproduct.

Язык: Английский

Процитировано

1

An overview on generation and general properties of N-heterocyclic carbenes: Applications of 1,2,4-triazolium carbenes as metal free organocatalysts DOI Creative Commons
Raphael Silva Moratório de Moraes, Maria Tereza Miranda Martins, Gabriel Tavares de Almeida Pinto

и другие.

Arabian Journal of Chemistry, Год журнала: 2023, Номер 17(2), С. 105527 - 105527

Опубликована: Дек. 16, 2023

N-Heterocyclic carbenes (NHCs) have been widely explored in the areas of catalysis, organometallic and medicinal chemistry. In particular, NHCs catalyze formation C-C C-heteroatom bounds with high regioselectivity stereoselectivity through umpolung non-umpolung processes for unconventional access to create a vast scope heterocycle molecules, including β-lactones, tetrahydroquinolines pyrroloquinoles. Here we summarized generation general properties NHC important NHC-catalyzed reactions, which typically involve species such as Breslow intermediates, homoenolates, enolates α, β-unsaturated acyl azoliums, among others. Examples aerobic oxidative/oxygenative carbene specifically highlighting reactions involving oxygen strategies employed activation NHC-catalytic are discussed detail. The catalytic use has one most powerful tools chemist's arsenal, applications commercially protocols. Given this context, relevance N-heterocyclic chemistry is described review.

Язык: Английский

Процитировано

3

One-pot synthesis of functionalized dihydropyridin-2-ones via carbene-catalyzed base-controlled [3+3] annulation reaction DOI
Zhan‐Yong Wang,

Guoyang Ma,

Yaoyao Xu

и другие.

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Herein, we have described a novel organocatalytic approach to access biologically important dihydropyridin-2-ones in one-pot way with generally high yields (up 99%) and excellent enantioselectivities 99% ee). This reaction proceeded

Язык: Английский

Процитировано

0

Expanded scope of chitin-derived nitrogen scaffolds enabled by the 3-acetamido-5-furfurylaldehyde (3A5F) platform DOI Creative Commons
Jessica C. Neville,

Christine N.Y. Kieu,

Jonathan Sperry

и другие.

Sustainable Chemistry and Pharmacy, Год журнала: 2024, Номер 42, С. 101838 - 101838

Опубликована: Ноя. 9, 2024

Язык: Английский

Процитировано

0

Unveiling the Hidden Reactivity in the N-Heterocyclic Carbene-Catalyzed Aerobic Oxidation of Aldehydes: Unlocking Its Powerful Catalytic Performance DOI

Chenrui Fan,

Xu Zhao,

Reveendra Gopireddy

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 2, 2024

An innovative solution that overcomes the long-standing inherently low efficiency in N-heterocyclic carbene-catalyzed aerobic oxidation of aldehydes is reported. This included design and synthesis a novel polymerized catalyst utilization flow reactor. The unprecedentedly high achieved via this protocol makes it synthetically applicable. A total turnover number (TON) 26,300 was based on recycling experiments (runs). highest TON single run could be up to 2475 with frequency (TOF) 208 h–1, far superior its traditional counterpart, which typical ranges from 20 100 TOF less than 10 h–1. has been recycled over 50 times still fully active. success attributed discovery hidden reactivity, observed for first time as an autoacceleration reaction rate during kinetic investigations. research also provided concrete evidence supporting conclusion radical intermediates played crucial roles catalytic cycle by having determinative impact overall rate.

Язык: Английский

Процитировано

0