Controllable Molecular Editing of 2-Amino-N-substituted Benzamides: Site-selective Synthesis of 6-Selenylated N-Substituted 1,2,3-Benzotriazine-4(3H)-ones

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 3, 2025

We present an efficient silver-catalyzed one-pot controllable molecular editing protocol for the transformation of 2-amino-N-substituted benzamides into 6-selenylated N-substituted 1,2,3-benzotriazine-4(3H)-ones under mild reaction conditions. This three-component strategy is achieved by building N-N/N═N/C-Se bonds, which provides a practical pathway preparation selenylated with broad substrate scope and good functional group tolerance, as well high site-selectivity. Mechanistic experiments suggest that this proceeds via intermolecular site-selective C-H selenylation readily available diselenides, followed annulation using AgNO3 nitrogen synthon.

Язык: Английский

---

Reimagining Dearomatization: Arenophile-Mediated Single-Atom Insertions and π-Extensions

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

ConspectusDearomatization of simple aromatics serves as one the most direct strategies for converting abundant chemical feedstocks into three-dimensional value-added products. Among such transformations, cycloadditions between arenes and alkenes have historically offered effective means to construct complex polycyclic architectures. However, traditionally harsh conditions, high-energy UV light irradiation, greatly limited scope this transformation. Nevertheless, recent progress has led development visible-light-promoted dearomative photocycloadditions with expanded capable preparing bicyclic structures.A fundamentally distinct approach involves visible-light activation arenophiles, which undergo para-photocycloaddition various aromatic compounds produce arene-arenophile cycloadducts. While only transiently stable subject retro-cycloaddition, further functionalization photocycloadducts allowed a wide collection dearomatization methodologies that access products orthogonal existing biological processes. Central strategy was observation photocycloaddition reveals π-system can be functionalized through traditional olefin chemistry. Coupled subsequent [4 + 2]-cycloreversion arenophile, process acts effectively isolate single from an ring. We developed several transformations bias methodology perform single-atom insertion π-extension reactions prepare unique cannot prepared easily means.Through application epoxidation, we were able develop method epoxidation pyridines arene-oxides pyridine-oxides, respectively. Notably, when arenophile chemistry is applied arenes, transposed site native olefinic reactivity, enabling site-selectivity functionalization. As result, oxygen (aza)arenes 3-benzoxepines. When applying in context cyclopropanations, accomplish cyclopropanation yield benzocycloheptatrienes upon cycloreversion. while Buchner ring expansion powerful carbon corresponding does not ring-expanded Furthermore, could utilized synthesis novel nanographenes M-region annulative (M-APEX) reaction. Traditionally, methods rely on reactivity at K- bay-region. arenophiles activate reactivity. arenophile-mediated diarylation, followed by cycloreversion, deliver π-extended exclusive selectivity.

Язык: Английский

---

ANROFRC Enables Skeletal Editing of 4-Arylpyrimidines into Diverse Nitrogen Heteroaromatics

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Март 25, 2025

Scaffold hopping is a key strategy in drug discovery. While one-to-one scaffold strategies are thriving and evolving, one-to-multiple remain challenging to design. We present here novel for the skeletal editing of pyrimidines into wide range heteroarenes through addition nucleophiles, ring-opening, fragmentation, ring-closing (ANROFRC) processes. This method features in situ generation vinamidinium salt intermediate, which serves as unique N-C-C-C four-atom (A4) synthon that reacts with A1 A2 synthons. Mechanistic studies reveal C4-aryl substituents play crucial role stabilizing intermediate. work provides powerful tool systematic construction modification nitrogen heterocycles, thereby expanding conventional molecular techniques.

Язык: Английский

---

Homologation of Alkenyl Carbonyls via a Cyclopropanation/Light‐Mediated Selective C‐C Cleavage Strategy

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Окт. 31, 2024

We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading selective cleavage more substituted carbon-carbon bond. Depending substrate structure, extended alkenes were isolated or directly reacted in a photo-Nazarov process bicyclic products. Based these results, unified reductive ring-opening reaction was developed by using diphenyl disulfide as hydrogen atom transfer (HAT) reagent. By performing sequential cyclopropanation/selective ring opening reaction, we achieved CH

Язык: Английский

---

A new route to the crinane skeleton via the low-valent titanium-mediated double reduction of cyclic sulfonamides

Tetrahedron Letters, Год журнала: 2024, Номер 150, С. 155285 - 155285

Опубликована: Авг. 31, 2024

The construction of a benzo-fused tetracyclic sulfonamide, followed by its low-valent titanium-based reduction and subsequent conversion to racemic crinane is reported. synthesis the sulfonamide features sulfonyl templated, regio- diastereoselective intramolecular Heck reaction, which installs an all-carbon quaternary centre. Thereafter, titanium removes group, liberating 3-aryloctahydroindole. A Pictet-Spengler reaction then generates targeted ethano-bridged phenanthridine core structure crinan alkaloids.

Язык: Английский

---

Homologation of Alkenyl Carbonyls via a Cyclopropanation/Light‐Mediated Selective C‐C Cleavage Strategy

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Окт. 31, 2024

Abstract We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading selective cleavage more substituted carbon‐carbon bond. Depending substrate structure, extended alkenes were isolated or directly reacted in a photo‐Nazarov process bicyclic products. Based these results, unified reductive ring‐opening reaction was developed by using diphenyl disulfide as hydrogen atom transfer (HAT) reagent. By performing sequential cyclopropanation/selective ring opening reaction, we achieved CH 2 insertion into α,β bond both acyclic and cyclic unsaturated compounds. Our protocol provides further tool for modification carbon framework organic compounds, complementing recent progress “skeletal editing”.

Язык: Английский

---