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

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Oct. 10, 2023

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. variety valuable amide-, ketone-, ester-, N-heterocycle-substituted unsymmetrical E-alkenes are synthesized in good yields high stereoselectivities. This mild method avoids use diazo compounds characterized by simple operation, step-economy, excellent chemoselectivity functional group compatibility. The combined experimental computational studies identify an amide-sulfoxonium ylide as a carbene precursor. Furthermore, comprehensive exploration reaction space also performed (600 reactions) model for yield prediction has been constructed.

Language: Английский

---

Recent Developments in Stereoselective Reactions of Sulfoxonium Ylides

Molecules, Journal Year: 2025, Volume and Issue: 30(3), P. 655 - 655

Published: Feb. 1, 2025

This review probes the recent developments in stereoselective reactions within area of sulfoxonium ylide chemistry since early 2000s. An abundance research has been applied to its emergence 1960s. There a continued effort then with work traditional areas, such as epoxidation, aziridination and cyclopropanation. Efforts have also novel olefination insertion reactions, develop methodologies using organocatalysis transition metal catalysis. The growing interrupted Johnson–Corey–Chaykovsky is described, whereby unexpected cyclopropanation epoxidation developed. In general, most observed mechanistic pathway ylides formal cycloaddition: (2 + 1) (e.g., epoxides, cyclopropanes, aziridines), (3 oxetanes, azetidines), (4 indanones, indolines). involves formation zwitterionic intermediate through nucleophilic addition carbanion an electrophilic site. intramolecular cyclization occurs, constructing cyclic product. Insertion X–H bonds X = S, N or P) are observed, protonation followed by X, form inserted

Language: Английский

---

Enantioselective synthesis of spiro-N,O-ketals via iridium and Brønsted acid co-catalyzed asymmetric formal [4+2] cycloaddition

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(11), P. 1448 - 1451

Published: Jan. 1, 2024

An asymmetric formal [4+2] cycloaddition of cyclic enamides with 2-(1-hydroxyallyl)phenol via iridium and Brønsted acid co-catalysis has been achieved to afford chiral N -unsubstituted spiro- , O -ketals.

Language: Английский

---

Recent Advances on the Catalytic Asymmetric Allylic α-Alkylation of Carbonyl Derivatives Using Free Allylic Alcohols

ACS Organic & Inorganic Au, Journal Year: 2024, Volume and Issue: 4(3), P. 269 - 286

Published: Feb. 10, 2024

During the last years, development of more sustainable and straightforward methodologies to minimize generation waste organic substances has acquired high importance within synthetic chemistry. Therefore, it is not surprising that many efforts are devoted ameliorating already well-known successful methodologies, is, case asymmetric allylic allylation reaction carbonyl compounds. The use free alcohols as alkylating agents in this transformation represents a step forward sense since minimizes production substrate manipulation. In review, we aim gather most recent describing strategy by paying special attention mechanisms, well their applications.

Language: Английский

---

Lithium Bromide-Promoted Formal C(sp³)–H Bond Insertion Reactions of β-Carbonyl Esters with Sulfoxonium Ylides to Synthesize 1,4-Dicarbonyl Compounds

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(10), P. 6974 - 6986

Published: May 4, 2024

A LiBr-promoted formal C(sp3)–H bond insertion reaction between β-carbonyl esters and sulfoxonium ylides is established. This practical has a wide range of substrate scope for both to give variety 1,4-dicarbonyl compounds with 43–94% yields. The features transition-metal-free conditions exclusive C-alkylation chemselectivity. use bench-stable overcomes previous methods that require transition metal as catalysts unstable diazo or toxic haloketones alkylation reagents.

Language: Английский

---

High-throughput experimentation and machine learning-promoted synthesis of α-phosphoryloxy ketones via Ru-catalyzed P(O)O-H insertion reactions of sulfoxonium ylides

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 10, 2024

Language: Английский

---

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

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(48)

Published: Oct. 10, 2023

Abstract 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. variety valuable amide‐, ketone‐, ester‐, N‐heterocycle‐substituted unsymmetrical E ‐alkenes are synthesized in good yields high stereoselectivities. This mild method avoids use diazo compounds characterized by simple operation, step‐economy, excellent chemoselectivity functional group compatibility. The combined experimental computational studies identify an amide‐sulfoxonium ylide as a carbene precursor. Furthermore, comprehensive exploration reaction space also performed (600 reactions) model for yield prediction has been constructed.

Language: Английский

---

Enantioselective synthesis of 2-amino-4H-chromene derivatives with antifungal activities on phytopathogenic fungi

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(13), P. 3692 - 3699

Published: Jan. 1, 2024

An Ir-catalyzed enantioselective cascade allylation/cyclization reaction of 2-(1-hydroxyallyl)phenols was developed, affording antifungal 2-amino-4 H -chromene derivatives with good to excellent enantioselectivities.

Language: Английский

---

Synthesis of Indolines via Palladium-Catalyzed [4+1] Annulation of (2-Aminophenyl) Methanols with Sulfoxonium Ylides

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(31), P. 6342 - 6351

Published: Jan. 1, 2024

A facile strategy for the synthesis of valuable indolines has been developed, involving a palladium(II)/Brønsted acid co-catalyzed annulation readily available (2-aminophenyl)methanols and sulfoxonium ylides. This protocol allows direct utilization OH group as leaving group, tolerates alkyl aryl groups on N atom aniline moiety, operates under mild reaction conditions, exhibits good efficiency.

Language: Английский

---

Direct synthesis of α-functionalized amides via heteroatom–hydrogen insertion reactions using amide-sulfoxonium ylides

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 25, 2024

α-Functionalized Si-, Ge-, B-, Se-, and S-amide moieties are present in many medicinally active molecules, but their synthesis remains challenging. Here, we demonstrate a high-throughput using amide-sulfoxonium ylides as carbene precursors Si-H, Ge-H, B-H, Se-H, S-H insertion reactions to target wide range of α-silyl, α-geryl, α-boryl, α-selenyl, α-sulfur (hetero)amides. The process is featured simple operation, mild conditions, broad substrate scope, high functional group compatibility, excellent chemoselectivity. Both experimental computational studies conducted explore the mechanisms underlying formation C-Si/Ge/B/Se/S bond. This research highlights use highly selective X-H with ylide-derived carbenes, paving way for preparation diverse organosilane, organogermane, organoboron, organoselenium, organosulfur compounds from accessible bench-stable precursors.

Language: Английский

---