Iron(II)‐Catalyzed 1,2‐Diamination of Styrenes Installing a Terminal NH2 Group Alongside Unprotected Amines DOI Creative Commons
Valentyn Pozhydaiev,

Antonio Paparesta,

Joseph Moran

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(45)

Published: July 17, 2024

Abstract 1,2‐Diamination of alkenes represents an attractive way to generate differentiated vicinal diamines, which are prevalent motifs in biologically active compounds and catalysts. However, existing methods usually limited scope produce diamines where one or both nitrogens protected, adding synthetic steps for deprotection further N‐functionalization reach a desired target. Furthermore, the range amino groups that can be introduced at internal position is fairly limited. Here we describe 1,2‐diamination styrenes directly installs free group terminal wide variety unprotected nitrogen nucleophiles (primary secondary alkyl aromatic amines, sulfoximines, N ‐heterocycles, ammonia surrogate) position. Two complementary sets conditions encompass electronically activated deactivated with diverse substitution patterns functional groups. Moreover, this strategy extended 1,2‐aminothiolation styrenes.

Language: Английский

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

62
Difunctionalization Processes Enabled by Hexafluoroisopropanol DOI Creative Commons
Maciej Piejko, Joseph Moran, David Lebœuf

et al.

ACS Organic & Inorganic Au, Journal Year: 2024, Volume and Issue: 4(3), P. 287 - 300

Published: March 4, 2024

In the past 5 years, hexafluoroisopropanol (HFIP) has been used as a unique solvent or additive to enable challenging transformations through substrate activation and stabilization of reactive intermediates. this Review, we aim at describing difunctionalization processes which were unlocked when HFIP was involved. Specifically, focus on cyclizations additions alkenes, alkynes, epoxides, carbonyls that introduce wide range functional groups interest.

Language: Английский

Citations

14
Modular and Practical 1,2‐Aryl(Alkenyl) Heteroatom Functionalization of Alkenes through Iron/Photoredox Dual Catalysis** DOI Creative Commons
Weigang Zhang, Tao Liu, Hwee Ting Ang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 13, 2023

Abstract Efficient methods for synthesizing 1,2‐aryl(alkenyl) heteroatomic cores, encompassing heteroatoms such as nitrogen, oxygen, sulfur, and halogens, are of significant importance in medicinal chemistry pharmaceutical research. In this study, we present a mild, versatile practical photoredox/iron dual catalytic system that enables access to highly privileged pharmacophores with exceptional efficiency site selectivity. Our approach exhibits an extensive scope, allowing the direct utilization wide range commodity or commercially available (hetero)arenes well activated unactivated alkenes diverse functional groups, drug scaffolds, natural product motifs substrates. By merging iron catalysis photoredox cycle, vast array alkene functionalization products incorporate neighboring azido, amino, halo, thiocyano nitrooxy group were secured. The scalability ability rapid synthesize numerous bioactive small molecules from readily starting materials highlight utility protocol.

Language: Английский

Citations

19
Stereospecific Synthesis of Unprotected, α,β-Disubstituted Tryptamines and Phenethylamines from 1,2-Disubstituted Alkenes via a One-Pot Reaction Sequence DOI
Duc Chu, Jonathan A. Ellman

Organic Letters, Journal Year: 2023, Volume and Issue: 25(20), P. 3654 - 3658

Published: May 12, 2023

Unprotected, α,β-disubstituted tryptamines and phenethylamines are obtained by a one-pot, metal-free sequence that proceeds the in situ formation of aziridinium salts followed Friedel–Crafts reaction with electron-rich (hetero)arenes. Both steps facilitated hexafluoroisopropanol as solvent. The one-pot was effective for diversely substituted indoles 1,3,5-trimethoxybenzene, cyclic acyclic alkenes, proceeded stereospecific fashion both (E)- (Z)-1,2-disubstituted alkenes. Moreover, morpholine addition to an salt provided diamine.

Language: Английский

Citations

14
Catalytic Synthesis of β‐(Hetero)arylethylamines: Modern Strategies and Advances DOI Creative Commons
Valentyn Pozhydaiev, Cyprien Muller, Joseph Moran

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)

Published: Aug. 21, 2023

Abstract β‐(Hetero)arylethylamines appear in a myriad of pharmaceuticals due to their broad spectrum biological properties, making them prime candidates for drug discovery. Conventional methods preparation often require engineered substrates that limit the flexibility synthetic routes and diversity compounds can be accessed. Consequently, provide rapid versatile access those scaffolds remain limited. To overcome these challenges, chemists have designed innovative modular strategies β‐(hetero)arylethylamine motif, paving way more extensive use future pharmaceuticals. This review outlines recent progresses synthesis (hetero)arylethylamines emphasizes how innovations enabled new levels molecular complexity, selectivity, practicality.

Language: Английский

Citations

13
Harnessing Bromo/Acyloxy Transposition (BrAcT) and Excited-State Copper Catalysis for Styrene Difunctionalization DOI
Upasana Mukherjee, Jagrut Shah, Djamaladdin G. Musaev

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21271 - 21279

Published: July 23, 2024

1,2-Difunctionalization of styrenes, adding two distinct functional groups across the C═C double bond, has emerged as a powerful tool for enhancing molecular complexity. Herein, we report development regioconvergent β-acyloxylation-α-ketonylation styrenes through bromo/acyloxy transposition (BrAcT) and excited-state copper catalysis. This approach is amenable to gram-scale synthesis tolerates wide range complex frameworks, including derivatives natural products marketed drugs. Our experimental computational studies suggest unique mechanism featuring dynamic, ionic BrAcT process copper-catalyzed redox reactions. We anticipate that this could serve broadly applicable versatile strategy β-acyloxylation-α-functionalization creating valuable intermediates preparing new pharmaceuticals, agrochemicals, materials.

Language: Английский

Citations

4
Oxydiazomethylation of Alkenes via Photoredox Catalysis DOI

Ying Zeng,

Xiaochan Zheng,

Lixing Shen

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

α-Diazoesters belong to significantly important carbenoid precursors in synthetic chemistry. Diazomethylation-based difunctionalization of alkenes is highly valuable but remain nontrivial. Herein, we reported a general and modular approach for the direct 1,2-oxydiazomethylation through visible-light photoredox catalysis. This process exploits photocatalyzed strategy convert γ-formyloxyl-α-diazoesters using α-diazo iodonium salts as carbyne precursors, featuring wide substrate tolerance broad late-stage diversifications. Mechanistic studies suggest that formation γ-carbocation-tethered α-diazoesters plays crucial role trapping DMF H

Language: Английский

Citations

4
Rh(III)-Catalyzed Diastereo- and Enantioselective Regiodivergent (Hetero)Arylamidation of (Homo)Allylic Sulfides DOI
Xiaoyan Jia,

Gui-Lin Hao,

Mengxia Feng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9768 - 9778

Published: March 28, 2024

A rhodium-catalyzed 3-component conjunctive diastereo- and regioselective arylamidation of (homo)allylic sulfides, organon boronic acids, dioxazolones is reported. These reactions deliver the 1,2-insertion 2,1-insertion products, respectively, for allylic sulfides homoallylic sulfides. The enantioselective terminal internal achieved, furnishing various 1,3-N,S compounds featuring one or two contiguous stereocenters in high yields with enantioselectivities. Mechanistic studies suggest a change turnover-limiting selectivity-determining steps induced by native easily removable sulfide group.

Language: Английский

Citations

3
Electrochemically‐Driven 1,4‐Aryl Migration via Radical Fluoromethylation of N‐Allylbenzamides: a Straightforward Access to Functionalized β‐Arylethylamines DOI Creative Commons
Étienne Derat, Géraldine Masson, Aurélie Claraz

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: April 30, 2024

An electrochemical radical Truce Smiles rearrangement of N-allylbenzamides is documented herein. The selective 1,4-aryl migration was triggered by the fluoromethylation alkene providing a direct route to fluoro derivatives highly privileged β-arylethylamine pharmacophore. This practical transformation utilizes readily available starting materials and employs an electrical current drive oxidative process under mild reaction conditions. It accommodates variety migratory aryl groups with different electronic properties substitution patterns. Careful selection protecting group on nitrogen atom N-allylbenzamide crucial outcompete undesired 6-endo cyclization achieve high level selectivity towards migration. DFT calculations support mechanism unveil origin between two competitive pathways.

Language: Английский

Citations

3
Photocatalyzed Azidofunctionalization of Alkenes via Radical‐Polar Crossover DOI Open Access
Pierre Palamini, Alexandre A. Schoepfer, Jérôme Waser

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical-polar crossover strategy. A broad range alkenes, including vinyl arenes, enamides, enol ethers, sulfides, dehydroamino esters, were regioselectively functionalized with an azide nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric oximes, phenols. method led to more efficient synthesis 1,2-azidofunctionalized pharmaceutical intermediates when compared previous approaches, resulting in both reduction step count increase overall yield. scope limitations these transformations further investigated through standard unbiased selection 15 substrate combinations out 1,175,658 possible clustering technique.

Language: Английский

Citations

0