Umpolung Synthesis of Selenoesters and Telluroesters via the Photoinduced Coupling of Acylsilanes with Electrophilic Chalcogen Reagents DOI
Ryosuke Masuda,

Yuki Anami,

Hiroyuki Kusama

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

A novel synthesis of selenoesters and telluroesters based on the reactions nucleophilic siloxycarbenes, which were generated by visible-light-induced isomerization corresponding aroyl-, heteroaroyl-, or alkenoylsilanes, with electrophilic chalcogen reagents was developed. The use appropriate selenides ditellurides/Lewis acids enabled coupling at temperatures below ambient temperature a broad substrate scope high functional-group tolerance. To best our knowledge, this is first example synthetic method for involving combination an acylanion equivalent cationic synthons.

Language: Английский

Divergent Synthesis of Fluoroalkyl Ketones through Controlling the Reactivity of Organoboronate Complexes DOI
Gang Zhou,

Zhuanzhuan Guo,

Shanshan Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 4026 - 4035

Published: Feb. 1, 2024

Herein, we report a divergent synthesis of fluoroalkyl ketones through visible-light-induced reactions between readily available organoboronic esters and acylsilanes. Selective control the reactivity in situ generated organoboronate complexes is key to achieving transformations. Under basic conditions, undergo deboronative fluoride elimination, resulting formation enol silyl ethers as intermediates that react with various electrophiles generate defluorinated products. Moreover, combination peroxide, 1,2-shift group favored over elimination ketal intermediates, leading This transition-metal-free reaction operationally simple, aryl, alkenyl, alkyl boronic are all suitable substrates. The synthetic potential has been demonstrated by gram-scale facile bioactive molecules including zifrosilone its analogs.

Language: Английский

Citations

25
Catalytic synthesis of β-lactam derivatives by carbonylative cycloaddition of acylsilanes with imines via a palladium Fischer-carbene intermediate DOI Creative Commons

Tetsuya Inagaki,

Takuya Kodama, Mamoru Tobisu

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(2), P. 132 - 138

Published: Jan. 15, 2024

Abstract Fischer-type carbene complexes are characterized by the presence of a π -donating group, such as an alkoxy group on carbon. Despite notable progress that has been made in synthetic methods involve use complexes, stoichiometric amounts still required for reactions and catalytic variants remain elusive. This limitation primarily stems from lack suitable precursors, which is sharp contrast to fact bearing electron-withdrawing can be readily generated corresponding diazo esters. Here we report acylsilanes function precursor Fischer-carbene complex action palladium catalyst. system used carbonylative cycloaddition with imines form densely substituted β-lactam derivatives. A key siloxycarbene–palladium intermediate was isolated successfully X-ray crystallography.

Language: Английский

Citations

16
Diastereoselective Synthesis of Monofluorocyclohexenes through Photocatalyzed Cascade Cyclization of gem‐Difluoroalkenes and α,β‐Unsaturated Carbonyl Compounds DOI
Zhengyu Li, Yizhi Zhang, Yunxiao Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 16, 2023

Monofluoroalkenes are nonhydrolyzable mimetics of amides. Previous work focused on the synthesis non-cyclic monofluoroalkenes. However, diastereoselective monofluorocyclohexenes from substrates is challenging. Herein, we report first photocatalyzed cascade cyclization reactions readily available α,β-unsaturated carbonyl compounds and gem-difluoroalkenes for highly functionalized monofluorocyclohexenes. The reaction shows broad substrate scope with high diastereoselectivity (>30 examples, up to 86 % yield, >20 : 1 dr). post-reaction transformations products demonstrate synthetic potential this methodology.

Language: Английский

Citations

24
Enantioselective Multifunctionalization with Rh Carbynoids DOI
Yu Qian,

Jie Tang,

Xiaoyu Zhou

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(48), P. 26403 - 26411

Published: Nov. 22, 2023

Multifunctionalization from the interception of active intermediates is an attractive synthetic strategy for efficient construction complex molecular scaffolds in atom and step economic fashion. However, design reactions involving metal carbynoids that exhibit carbene/carbocation behavior currently limited, developing catalyst-controlled highly enantioselective versions poses significant challenges. In this study, we present first asymmetric trifunctionalization with rhodium carbynoids. This reaction unveils distinctive reactivity carbynoid precursor, enabling it to react simultaneously two nucleophiles one electrophile. process involves formation distinct carbene ylides alcohol/carbamate trapping ylide imine, resulting three new bonds. Furthermore, allows divergent synthesis a wide array β-amino esters high yields exceptional enantioselectivity.

Language: Английский

Citations

24
Radical Brook rearrangement: past, present, and future DOI
Yunxiao Zhang, Gang Zhou, Shanshan Liu

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review aims to provide an overview of radical Brook rearrangement, which is organized by grouping three type reactive species generated via the unique rearrangement process.

Language: Английский

Citations

1
The Indenyl Effect: Accelerated C−H Amidation of Arenes via Ind*RhIII Nitrene Transfer Catalysis** DOI Creative Commons
Liselle Atkin, Daniel L. Priebbenow

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 6, 2023

Investigations into C-H amidation reactions catalysed by cationic half-sandwich d6 metal complexes revealed that the indenyl-derived catalyst [Ind*RhCl2 ]2 significantly accelerated directed ortho of benzoyl silanes using 1,4,2-dioxazol-5-ones. Ring slippage involving a haptotropic η5 to η3 rearrangement indenyl complex proposedly enables ligand substitution at centre proceed via associative, rather than dissociative pathways, leading significant rate and yield enhancements. Intriguingly, this phenomenon appears specific for weakly coordinating carbonyl-based directing groups with no acceleration observed corresponding strongly nitrogen-based groups.

Language: Английский

Citations

17
Visible-Light-Induced Siloxycarbene Addition to N═N of Azodicarboxylates: Synthesis of Acyl Hydrazides from Acylsilanes DOI
Mohammad Saleem,

Akash Ratwan,

Pokhriyal Yamini

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(10), P. 2039 - 2044

Published: March 4, 2024

We report the synthesis of acyl hydrazides from acylsilanes in presence visible light without aid additives or transition metals. Acylsilanes underwent [1,2]-Brook rearrangement to generate nucleophilic siloxycarbenes which on further addition N═N azodicarboxylates produced hydrazides. Control experiments indicate that reaction proceeds through singlet carbene intermediate. Transformation hydrazide functionality other functional groups was demonstrated, including drug candidate Moclobemide.

Language: Английский

Citations

7
Chemoselective Synthesis of Unsymmetrical Dithioacetals through Sequential Carbene Insertion and Acetal Exchange of Acylsilanes and Thiols under Visible Light Irradiation DOI
Wang Zhang, Danni Yang,

Dou-Dou Guo

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(6), P. 1282 - 1286

Published: Feb. 1, 2024

Dithioacetals are a frequently used motif in synthetic organic chemistry, and most existing reports discuss only symmetrical dithioacetals. Examples of unsymmetrical dithioacetals scarce, few general methods for the selective synthesis these compounds exists. An intriguing visible-light-induced strategy has been established this work sequential reactions S–H insertion acetal exchange between acylsilanes two different thiols that deliver wide variety moderate yields. The were obtained with high selectivity, great functional groups tolerated.

Language: Английский

Citations

6
Stereoselective Synthesis of Silyl Enol Ethers with Acylsilanes and α,β-Unsaturated Ketones DOI
Ying Liu, Zhihong Zhu, Yunxiao Zhang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(28), P. 5911 - 5916

Published: July 8, 2024

Acylsilanes are emerging bench-stable reagents for the generation of electron-rich oxycarbenes that difficult to access with unstable diazo compounds. Herein, we report a siloxycarbene-mediated stereoselective synthesis silyl enol ethers through visible-light-induced intermolecular reactions between acylsilanes and α,β-unsaturated ketones. Both solvent low temperature important success reaction. This approach features atomic economics, exclusive stereocontrol, broad substrate scope. The synthetic potential this methodology is demonstrated by gram-scale reaction various downstream transformations including requiring configuration purity ethers.

Language: Английский

Citations

6
Visible-light-promoted defluorinated alkylation of trifluoromethyl alkenes initiated by radical [1,2]-Brook rearrangement: facile synthesis ofgem-difluoro homoallylic alcohol derivatives DOI
Tao Qin,

Chunlu Xu,

Ge Zhang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(8), P. 1981 - 1987

Published: Jan. 1, 2023

A photoinduced radical [1,2]-Brook rearrangement/defluorinated alkylation reaction of α-trifluoromethyl alkenes with α-silyl alcohols was developed for facile access to gem -difluoro homoallylic alcohol derivatives.

Language: Английский

Citations

14