Visible‐Light‐Induced Iminothiolation of Unactivated Alkenes

Wang, Dingxing; Cai, Sai‐Hu; Liu, Haidong; Lu, Ye; Zhu, Caixia; Feng, Chao

doi:10.1002/ajoc.202100107

Cited by 6 publications

References 63 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Cyclization Reactions of Nitrogen‐Centered Radicals

McCombie¹,

Quiclet‐Sire²,

Zard³

2021

Organic Reactions

View full text Add to dashboard Cite

The cyclization of nitrogen‐centered radicals constitutes a powerful approach for the synthesis of a broad variety of nitrogen heterocycles. As with carbon‐centered radicals, the most common ring‐closure mode is the 5‐ exo cyclization onto an internal unsaturation, and the stereoselectivity is similar. Numerous methods for the generation of almost every type of nitrogen‐centered radical have been described. They involve the direct or indirect rupture of N–Y bonds, with Y = halogen (except fluorine), oxygen, nitrogen, sulfur, and hydrogen. Indirect methods, such as the addition of carbon radicals to imines, azides, and nitriles, have also been devised. The extended choice of methods and precursors, and the general mildness of the experimental conditions and tolerance for numerous functional groups, represent valuable synthetic advantages. Furthermore, the cyclization step can be part of a radical cascade leading to multiple bond formations and the rapid construction of complex molecular frameworks. This chapter describes the types, structures, and reactivity of nitrogen‐centered radicals, and details the mechanistic basis of the methods used to generate them. The methods include stannane‐based processes, oxidations and reductions by single‐electron transfer, thermolysis, electrolysis, photolysis, and photoredox catalysis. The factors that influence the stereoselectivity of the ring‐closures are discussed briefly. Applications to the total synthesis of natural products, as well as functional‐group compatibilities, reaction variants, and comparison to other methods for the synthesis of nitrogen heterocycles by ionic, organometallic, and uncatalyzed ring‐closures onto alkenes are also presented. The tabular surveys are organized according to the type of nitrogen‐centered radical involved in the cyclization step: aminyls, amidyls, carbamyls, iminyls, amidinyls, and other types of nitrogen‐centered radicals.

show abstract

Cyclization Reactions of Nitrogen‐Centered Radicals

McCombie¹,

Quiclet‐Sire²,

Zard³

2021

Organic Reactions

View full text Add to dashboard Cite

show abstract

Imino‐Fluoroalkanesulfonylation of γ,δ‐Unsaturated Oxime Esters Enabled by Photoredox/Cu Dual Catalysis

Li,

Chen,

Xie

et al. 2023

Asian J Org Chem

View full text Add to dashboard Cite

Sulfonyl‐tethered N‐containing heterocycles are valuable building blocks in synthetic and pharmaceutical chemistry. Recently, the installation of fluoroalkanesulfonyl groups into heterocycles via the difunctionalization of alkenes still remains challenging. Herein in this work, an imino‐fluoroalkanesulfonylation of γ,δ‐unsaturated oxime esters has been achieved via photoredox/Cu dual catalysis. A variety of fluoroalkanesulfonyl‐tethered pyrroline derivatives have been readily synthesized in moderate to good yields under mild conditions.

show abstract

Photocatalytic Multisite Functionalization of Unactivated Terminal Alkenes by Merging Polar Cycloaddition and Radical Ring‐Opening Process

Liu,

Wang,

Wang

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

Although highly appealing for rapid access of molecular complexity, multi‐functionalization of alkenes that allows incorporation of more than two functional groups remains a prominent challenge. Herein, we report a novel strategy that merges dipolar cycloaddition with photoredox promoted radical ring‐opening remote C(sp3)–H functionalization, thus enabling a smooth 1,2,5‐trifunctionalization of unactivated alkenes. A highly regioselective [3+2] cycloaddition anchors a reaction trigger onto alkene substrates. The subsequent halogen atom transfer (XAT) selectively initiates ring‐opening process, which is followed by a series of 1,5‐hydrogen atom transfer (1,5‐HAT) and intermolecular fluorine atom transfer (FAT) events. With this method, site‐selective introduction of three different functional groups is accomplished and a broad spectrum of valuable β‐hydroxyl‐ε‐fluoro‐nitrile products are synthesized from readily available terminal alkenes.

show abstract

Visible‐Light‐Induced Iminothiolation of Unactivated Alkenes

Cited by 6 publications

References 63 publications

Cyclization Reactions of Nitrogen‐Centered Radicals

Cyclization Reactions of Nitrogen‐Centered Radicals

Imino‐Fluoroalkanesulfonylation of γ,δ‐Unsaturated Oxime Esters Enabled by Photoredox/Cu Dual Catalysis

Photocatalytic Multisite Functionalization of Unactivated Terminal Alkenes by Merging Polar Cycloaddition and Radical Ring‐Opening Process

Contact Info

Product

Resources

About