Diastereoselective Homocoupling of Benzylic C(sp3)–H Bonds Enabled by Halogen Transfer DOI
Xirong Liu, Xin An, Xue Zhao

и другие.

Organic Letters, Год журнала: 2024, Номер 26(43), С. 9257 - 9262

Опубликована: Окт. 18, 2024

A transition-metal- and harsh-oxidant-free strategy for diastereoselective homocoupling of benzylic α-boryl carbanions has been developed. Central to this methodology is the ability halogen transfer reagent seamlessly integrate halogenation substitution within a compatible process. Additionally, also applicable diarylmethanes alkylheteroarenes. Substrates bearing oxidatively sensitive functional groups were well-tolerated. Preliminary studies suggest that hydrogen bond between two boryl contributes high diastereoselectivities.

Язык: Английский

Direct Benzylic C–H Etherification Enabled by Base‐Promoted Halogen Transfer DOI

Kendelyn I. Bone,

Thomas R. Puleo,

Michael D. Delost

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 21, 2024

We disclose a benzylic C-H oxidative coupling reaction with alcohols that proceeds through synergistic deprotonation, halogenation and substitution sequence. The combination of tert-butoxide bases 2-halothiophene halogen oxidants enables the first general protocol for generating using benzyl halides deprotonative pathway. In contrast to existing radical-based methods functionalization, this process is guided by acidity trends. This gives rise new synthetic capabilities, including ability functionalize diverse methyl(hetero)arenes, tolerance oxidizable nucleophilic functional groups, precision site-selectivity polyalkylarenes use double etherification controllably oxidize methylarenes benzaldehydes.

Язык: Английский

Процитировано

5
Annulation-induced hidden reactivity of N-(2-ethynylaryl)-1,2,3-triazoles to cinnolines under microwave irradiation DOI Creative Commons

Yangang Wu,

Chaewon Yi,

L.‐G. LIN

и другие.

Green Synthesis and Catalysis, Год журнала: 2025, Номер unknown

Опубликована: Март 1, 2025

Язык: Английский

Процитировано

0
Direct Benzylic C–H Etherification Enabled by Base-Promoted Halogen Transfer DOI Creative Commons

Kendelyn I. Bone,

Thomas R. Puleo,

Michael D. Delost

и другие.

Опубликована: Март 29, 2024

We disclose a benzylic C–H oxidative coupling reaction with alcohols that proceeds through synergistic deprotonation, halogenation and substitution sequence. The combination of tert-butoxide bases 2-halothiophene halogen oxidants enables the first general protocol for generating using benzyl halides deprotonative pathway. In contrast to existing radical-based pathways functionalization, this process is guided by acidity trends. This gives rise new synthetic capabilities, including ability functionalize diverse methyl(hetero)arenes, tolerance oxidizable nucleophilic functional groups, precision regioselectivity polyalkylarenes use double etherification controllably oxidize methylarenes benzaldehydes.

Язык: Английский

Процитировано

1
6‐Hydroxy Picolinohydrazides Promoted Cu(I)‐Catalyzed Hydroxylation Reaction in Water: Machine‐Learning Accelerated Ligands Design and Reaction Optimization DOI
Lanting Xu, Jiazhou Zhu, Xiaodong Shen

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(52)

Опубликована: Авг. 27, 2024

Hydroxylated (hetero)arenes are privileged motifs in natural products, materials, small-molecule pharmaceuticals and serve as versatile intermediates synthetic organic chemistry. Herein, we report an efficient Cu(I)/6-hydroxy picolinohydrazide-catalyzed hydroxylation reaction of (hetero)aryl halides (Br, Cl) water. By establishing machine learning (ML) models, the design ligands optimization conditions were effectively accelerated. The N-(1,3-dimethyl-9H- carbazol-9-yl)-6-hydroxypicolinamide (L32, 6-HPA-DMCA) demonstrated high efficiency for bromides, promoting reactions with a minimal catalyst loading 0.01 mol % (100 ppm) at 80 °C to reach 10000 TON; substrates containing sensitive functional groups, needs be increased 3.0 under near-room temperature conditions. N-(2,7-Di-tert-butyl-9H-carbazol-9-yl)-6-hydroxypicolinamide (L42, 6-HPA-DTBCA) displayed superior activity chloride substrates, enabling 100 2-3 loading. These represent state art both lowest copper-catalyzed reactions. Furthermore, this method features sustainable environmentally friendly solvent system, accommodates wide range shows potential developing robust scalable synthesis processes key pharmaceutical intermediates.

Язык: Английский

Процитировано

1
Aryne Aminohalogenation Using Protic Amines Enabled by Halogen Transfer DOI
Joshua Gavin,

Lars Anderson,

Courtney C. Roberts

и другие.

Organic Letters, Год журнала: 2024, Номер 26(36), С. 7530 - 7534

Опубликована: Авг. 28, 2024

Methods for aryne difunctionalization have been the focus of recent research, but one limitation is use nucleophiles with proton sources. Herein, we demonstrate halogen transfer reagents to enable protic amines in aminohalogenation difunctionalizations up 86% yield. This method uses and arynes a variety N-heterocyclic scaffolds. Through derivatizations, synthetic utility these products demonstrated.

Язык: Английский

Процитировано

1
Transition Metal–Free Synthesis of Vinyl Nitriles from Aldehydes with Acetonitrile at Room Temperature DOI
Qing Li, Wenjing Liu,

Yuyao Xie

и другие.

ChemistrySelect, Год журнала: 2024, Номер 9(36)

Опубликована: Сен. 19, 2024

Abstract A simple and mild protocol for the direct synthesis of vinyl nitriles is described. By employing potassium trimethylsilanolate as base benzyl chloride efficient promoter, a series E‐configured are selectively obtained from readily available aldehydes acetonitrile at room temperature without aid transition metal catalyst. Mechanistical investigations reveal that this transformation may go through Knoevenagel condensation process.

Язык: Английский

Процитировано

1
Base-Promoted Direct C–H Hydroxylation of N-Heteroarenes DOI
Paul Richardson

Synfacts, Год журнала: 2024, Номер 20(07), С. 0682 - 0682

Опубликована: Июнь 14, 2024

Key words halogen transfer - hydroxylation pyridines 1,3-azoles electron-deficient arenes

Язык: Английский

Процитировано

0
Direct Benzylic C–H Etherification Enabled by Base‐Promoted Halogen Transfer DOI

Kendelyn I. Bone,

Thomas R. Puleo,

Michael D. Delost

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(39)

Опубликована: Июнь 28, 2024

Abstract We disclose a benzylic C−H oxidative coupling reaction with alcohols that proceeds through synergistic deprotonation, halogenation and substitution sequence. The combination of tert ‐butoxide bases 2‐halothiophene halogen oxidants enables the first general protocol for generating using benzyl halides deprotonative pathway. In contrast to existing radical‐based methods functionalization, this process is guided by acidity trends. This gives rise new synthetic capabilities, including ability functionalize diverse methyl(hetero)arenes, tolerance oxidizable nucleophilic functional groups, precision site‐selectivity polyalkylarenes use double etherification controllably oxidize methylarenes benzaldehydes.

Язык: Английский

Процитировано

0
6‐Hydroxy Picolinohydrazides Promoted Cu(I)‐Catalyzed Hydroxylation Reaction in Water: Machine‐Learning Accelerated Ligands Design and Reaction Optimization DOI
Lanting Xu, Jiazhou Zhu, Xiaodong Shen

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(52)

Опубликована: Авг. 27, 2024

Abstract Hydroxylated (hetero)arenes are privileged motifs in natural products, materials, small‐molecule pharmaceuticals and serve as versatile intermediates synthetic organic chemistry. Herein, we report an efficient Cu(I)/6‐hydroxy picolinohydrazide‐catalyzed hydroxylation reaction of (hetero)aryl halides (Br, Cl) water. By establishing machine learning (ML) models, the design ligands optimization conditions were effectively accelerated. The N ‐(1,3‐dimethyl‐9 H ‐ carbazol‐9‐yl)‐6‐hydroxypicolinamide ( L32 , 6‐HPA‐DMCA) demonstrated high efficiency for bromides, promoting reactions with a minimal catalyst loading 0.01 mol % (100 ppm) at 80 °C to reach 10000 TON; substrates containing sensitive functional groups, needs be increased 3.0 under near‐room temperature conditions. ‐(2,7‐Di‐ tert ‐butyl‐9 ‐carbazol‐9‐yl)‐6‐hydroxypicolinamide L42 6‐HPA‐DTBCA) displayed superior activity chloride substrates, enabling 100 2–3 loading. These represent state art both lowest copper‐catalyzed reactions. Furthermore, this method features sustainable environmentally friendly solvent system, accommodates wide range shows potential developing robust scalable synthesis processes key pharmaceutical intermediates.

Язык: Английский

Процитировано

0
Diastereoselective Homocoupling of Benzylic C(sp3)–H Bonds Enabled by Halogen Transfer DOI
Xirong Liu, Xin An, Xue Zhao

и другие.

Organic Letters, Год журнала: 2024, Номер 26(43), С. 9257 - 9262

Опубликована: Окт. 18, 2024

A transition-metal- and harsh-oxidant-free strategy for diastereoselective homocoupling of benzylic α-boryl carbanions has been developed. Central to this methodology is the ability halogen transfer reagent seamlessly integrate halogenation substitution within a compatible process. Additionally, also applicable diarylmethanes alkylheteroarenes. Substrates bearing oxidatively sensitive functional groups were well-tolerated. Preliminary studies suggest that hydrogen bond between two boryl contributes high diastereoselectivities.

Язык: Английский

Процитировано

0