HTE and machine learning-assisted development of iridium(<scp>i</scp>)-catalyzed selective O–H bond insertion reactions toward carboxymethyl ketones

Xu, Yougen; Ren, Feixiao; Su, Lebin; Xiong, Zhitao; Zhu, Xinwei; Lin, Xinyuan; Qiao, Nan; Tian, Hao; Tian, Chaoguang; Liao, Kuangbiao

doi:10.1039/d2qo01954j

“…Sulfoxonium ylides, which usually have analogous reactivity and better stability compared with diazo compounds, have attracted increasingly significant interest in modern organic transformations . For example, transition-metal-catalyzed O–H functionalization of sulfoxonium ylides with carboxylic acids (Scheme e) has been developed. − Nevertheless, potentially different reactivity between sulfoxonium ylides and diazo compounds should be further examined . Herein, a photoredox-catalyzed O–H insertion of sulfoxonium ylides with carboxylic acids to construct α-acyloxy ketones is realized via a proton-assisted electron transfer strategy under mild conditions (Scheme f).…”

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confidence: 99%

Construction of α-Acyloxy Ketones via Photoredox-Catalyzed O–H Insertion of Sulfoxonium Ylides with Carboxylic Acids

Sun,

Peng,

Wang

et al. 2023

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High‐Throughput Experimentation and Machine Learning‐Assisted Optimization of Iridium‐Catalyzed Cross‐Dimerization of Sulfoxonium Ylides

Xu,

Gao,

Su

et al. 2023

Angewandte Chemie

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A novel and convenient approach that combines high‐throughput experimentation (HTE) with machine learning (ML) technologies to achieve the first selective cross‐dimerization of sulfoxonium ylides via iridium catalysis is presented. A variety of valuable amide‐, ketone‐, ester‐, and N‐heterocycle‐substituted unsymmetrical E‐alkenes are synthesized in good yields with high stereoselectivities. This mild method avoids the use of diazo compounds and is characterized by simple operation, high step‐economy, and excellent chemoselectivity and functional group compatibility. The combined experimental and computational studies identify an amide‐sulfoxonium ylide as a carbene precursor. Furthermore, a comprehensive exploration of the reaction space is also performed (600 reactions) and a machine learning model for reaction yield prediction has been constructed.

show abstract

High‐Throughput Experimentation and Machine Learning‐Assisted Optimization of Iridium‐Catalyzed Cross‐Dimerization of Sulfoxonium Ylides

Xu,

Gao,

Su

et al. 2023

Self Cite

View full text Add to dashboard Cite

A novel and convenient approach that combines high‐throughput experimentation (HTE) with machine learning (ML) technologies to achieve the first selective cross‐dimerization of sulfoxonium ylides via iridium catalysis is presented. A variety of valuable amide‐, ketone‐, ester‐, and N‐heterocycle‐substituted unsymmetrical E‐alkenes are synthesized in good yields with high stereoselectivities. This mild method avoids the use of diazo compounds and is characterized by simple operation, high step‐economy, and excellent chemoselectivity and functional group compatibility. The combined experimental and computational studies identify an amide‐sulfoxonium ylide as a carbene precursor. Furthermore, a comprehensive exploration of the reaction space is also performed (600 reactions) and a machine learning model for reaction yield prediction has been constructed.

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HTE and machine learning-assisted development of iridium(i)-catalyzed selective O–H bond insertion reactions toward carboxymethyl ketones

Abstract: Functional group substituted carboxymethyl ketones, especially heterocyclic ones, are important structural motifs for biologically active molecules, but their synthesis is challenging. In this work, by combining HTE and machine learning...

Cited by 12 publications

References 42 publications

Construction of α-Acyloxy Ketones via Photoredox-Catalyzed O–H Insertion of Sulfoxonium Ylides with Carboxylic Acids

Construction of α-Acyloxy Ketones via Photoredox-Catalyzed O–H Insertion of Sulfoxonium Ylides with Carboxylic Acids

High‐Throughput Experimentation and Machine Learning‐Assisted Optimization of Iridium‐Catalyzed Cross‐Dimerization of Sulfoxonium Ylides

High‐Throughput Experimentation and Machine Learning‐Assisted Optimization of Iridium‐Catalyzed Cross‐Dimerization of Sulfoxonium Ylides

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