Three-Component Photochemical 1,2,5-Trifunctionalizations of Alkenes toward Densely Functionalized Lynchpins DOI
Fritz Paulus, Colin Stein,

Corinna Heusel

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(43), P. 23814 - 23823

Published: Oct. 18, 2023

Radical remote 1,n-difunctionalization reactions (n > 2) of alkenes are powerful tools to efficiently introduce functional groups with selected distances into target molecules. Among these reactions, 1,5-difunctionalizations an important subclass, leading sought-after scaffolds, but typically suffer from tailored starting materials and strict limitations for the formed group in 2-position. Seeking address issues make radical more applicable, we report a novel three-component 1,2,5-trifunctionalization reaction between imine-based bifunctional reagents two distinct alkenes, driven by visible light energy transfer-catalysis. Key achieving this selective one-step installation three different via choreographed formation four bonds was utilization 1,2-boron shift rigorous capitalization polarities stabilities. Thorough mechanistic studies were carried out, synthetic utility obtained products demonstrated various downstream modifications. Notably, addition functionalization individual groups, their interplay gave rise unique array cyclic products.

Language: Английский

Energy transfer photocatalysis: exciting modes of reactivity DOI
Subhabrata Dutta, Johannes E. Erchinger, Felix Strieth‐Kalthoff

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(3), P. 1068 - 1089

Published: Jan. 1, 2024

Leveraging light energy to expose the ‘dark’ reactive states describes whole essence of triplet–triplet transfer. This offers an impressive opportunity conduct a multitude diverse reactions and access sought-after molecular motifs.

Language: Английский

Citations

136
EnT-Mediated N–S Bond Homolysis of a Bifunctional Reagent Leading to Aliphatic Sulfonyl Fluorides DOI
Johannes E. Erchinger,

Reece Hoogesteger,

Ranjini Laskar

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(4), P. 2364 - 2374

Published: Jan. 18, 2023

Sulfur(VI) fluoride exchange (SuFEx) gives rise to a plethora of high-valent sulfur linkages; however, the availability (aliphatic) sulfonyl manifolds lag behind, owing limited sources introducing SO2F moiety via classical two-electron approach. Recently, radical-based methodologies have emerged as complementary strategy increase diversity accessible click partners. In this work, synthesis bench-stable sulfamoyl reagent is presented, which may undergo sigma-bond homolysis upon visible-light-induced sensitization form protected β-amino fluorides from alkene feedstocks. Notably, offers an appealing access various building blocks for peptido fluorides, relevant in medicinal chemistry context, well intriguing entry β-ammonium sulfonates and β-sultams, alkenes. Densely functionalized 1,3-sultones were obtained by employing allyl alcohols substrates. Surprisingly, chloride-derived β-imino underwent S-O bond formation ring closure yield rigid cyclopropyl sulfonate ester under SuFEx conditions. Furthermore, engaging thiol-based hydrogen atom donor reaction, reactivity same can be tuned toward direct aliphatic fluorides. Mechanistic experiments indicate energy transfer (EnT)-mediated process. The transient radical adds product occurs either radical-radical coupling or (HAT), respectively.

Language: Английский

Citations

92
Metal-Free Amino(hetero)arylation and Aminosulfonylation of Alkenes Enabled by Photoinduced Energy Transfer DOI

Xu-Kuan Qi,

Mengjie Zheng, Chao Yang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(30), P. 16630 - 16641

Published: July 24, 2023

β-(Hetero)arylethylamines are privileged structural motifs found in many high-value organic molecules, including pharmaceuticals and natural products. To construct these important molecular skeletons, previous methods mainly achieved by amino(hetero)arylation reaction with the aid of transition metals preactivated substrates. Herein, we report a metal-free photoinduced intermolecular for single-step installation both (hetero)aryl iminyl groups across alkenes an efficient regioselective manner. This method shows broad scope (up to 124 examples) excellent tolerance various olefins─from simplest ethylene complex multisubstituted can all participate reaction. Furthermore, aminosulfonylation be also conducted presence sodium bisulfite as SO2 source.

Language: Английский

Citations

59
Photoredox/HAT-Catalyzed Dearomative Nucleophilic Addition of the CO2 Radical Anion to (Hetero)Aromatics DOI
Saeesh R. Mangaonkar, Hiroki Hayashi, Hideaki Takano

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(4), P. 2482 - 2488

Published: Feb. 3, 2023

The radical anion of CO2 (CO2•–) is a strongly nucleophilic species with rapidly emerging applications in contemporary organic chemistry. This exhibits high reactivity single-electron reduction reactions due to the concomitant release stable CO2, or Giese-type reactions, especially for electron-deficient alkenes and styrene derivatives. In contrast previous reports, we herein disclose development robust method introduction CO2•–, which can be generated from cesium formate under photoredox/hydrogen atom transfer (HAT) catalysis, into heteroaromatics such as benzofuran, benzothiophene, indole derivatives afford synthetically useful α-oxy, α-thio, α-amino acid moderate yield. addition, when using naphthalene derivatives, both addition occur simultaneously produce carboxylated tetrahydronaphthalene good Moreover, one tetrahydronaphthalenes that bear cyano group was transformed corresponding γ-butyrolactam via functionality through hydrogenation followed by cyclization. To best our knowledge, these dearomative carboxylation metal formates photoredox/HAT conditions are unprecedented, thus providing synthetic option C1 source (hetero)aromatics.

Language: Английский

Citations

50
The impact of UV light on synthetic photochemistry and photocatalysis DOI
Giulio Goti, Kavyasree Manal, Jayaraman Sivaguru

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(5), P. 684 - 692

Published: March 1, 2024

Language: Английский

Citations

38
Ti-Catalyzed Formal [2π + 2σ] Cycloadditions of Bicyclo[1.1.0]butanes with 2-Azadienes to Access Aminobicyclo[2.1.1]hexanes DOI

Haosong Ren,

Tianxiang Li,

Jinping Xing

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1745 - 1750

Published: Feb. 20, 2024

Saturated bicyclic amines are increasingly targeted to the pharmaceutical industry as sp3-rich bioisosteres of anilines. Numerous strategies have been established for preparation bridgehead aminobicyclics. However, methods assemble bridge-amino hydrocarbon skeleton, which serves a meta-substituted arene bioisostere, limited. Herein, general approach access 2-aminobicyclo[2.1.1]hexanes (aminoBCHs) by titanium-catalyzed formal [2π + 2σ] cycloaddition bicyclo[1.1.0]butanes and 2-azadienes was developed. Simple derivatization aminoBCHs leads various medicinally agrochemically important analogues.

Language: Английский

Citations

33
γ-Amino Alcohols via Energy Transfer Enabled Brook Rearrangement DOI Creative Commons
Ranjini Laskar, Subhabrata Dutta, Jan C. Spies

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10899 - 10907

Published: April 3, 2024

In the long-standing quest to synthesize fundamental building blocks with key functional group motifs, photochemistry in recent past has comprehensively established its attractiveness. Amino alcohols are not only functionally diverse but ubiquitous biologically active realm of compounds. We developed bench-stable bifunctional reagents that could then access sparsely reported γ-amino directly from feedstock alkenes through energy transfer (EnT) photocatalysis. A designed 1,3-linkage across is made possible by intervention a radical Brook rearrangement takes place downstream EnT-mediated homolysis our reagent(s). combination experimental mechanistic investigations and detailed computational studies (DFT) indicates chain propagated reaction pathway.

Language: Английский

Citations

24
Radical 1,2-Nitrogen Migration Cascades of β-Bromo α-Amino Acid Esters to Access β-Amino Acid Motifs Enabled by Cooperative Ni/Diboron Catalysis DOI

Yu Hong,

Zi-Cheng Liao,

Jiajie Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 5491 - 5502

Published: March 28, 2024

Amino acid esters serve as crucial intermediates in protein synthesis and common structural elements biologically active natural compounds. Herein, we present an efficient radical cascade reaction involving 1,2-nitrogen migration C(sp2)–H intramolecular cyclization, enabling access to a diverse array of β-amino motifs. Upon cooperative Ni/diboron catalysis, π-system-independent 1,2-N-shift β-bromo α-amino is achieved, which allows the formation two new bonds, including C(sp3)–C(sp2) bond C(sp3)–N bond. The exhibits extensive substrate compatibility high diastereoselectivity proceeds without need for oxidants, toxic initiators, and/or elevated temperatures. It has been observed that diboron compounds both activating reagent inert C–N cleavage/migration reductant Ni catalytic cycle. This sheds light on remote N-functionalities π-systems. cascades followed by intermolecular halogenation or selenation are also demonstrated.

Language: Английский

Citations

21
Energy-transfer photocatalysis for Minisci C–H (amino)alkylation of heteroarenes using oxime esters as dual-role reagents DOI
Jun Xu, Yu‐Ru Zhang,

Ruiyuan Xu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(18), P. 5122 - 5129

Published: Jan. 1, 2024

This study demonstrates a strategy involving photoinduced energy transfer for decarboxylative Minisci C–H (amino)alkylation of heteroarenes employing diverse oxime esters (from carboxylic acids) as (amino)alkylating reagents.

Language: Английский

Citations

16
Photoredox-Catalyzed Alkene Acylesterification with Acyloxime Esters via C–C and Tertiary C–O Bond Formation DOI

Youkang Zhou,

Ruiying Zhao, Mingyou Hu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

We describe an efficient acyl esterification method for alkenes utilizing acyloxime esters as bifunctional reagents featuring radical acylation and congested C–O bond formation. This approach is characterized by mild photoredox conditions, high step atom economy, a broad substrate scope, excellent regioselectivity. A variety of valuable α-acyl hindered alcohol esters, including those obtained via gram-scale synthesis late-stage functionalization pharmaceutical molecules, were presented, demonstrating its synthetic potential practicability.

Language: Английский

Citations

3