Visible Light-Induced Reactions of Diazo Compounds and Their Precursors

Chemical Reviews, Год журнала: 2024, Номер 124(11), С. 7214 - 7261

Опубликована: Май 16, 2024

In recent years, visible light-induced reactions of diazo compounds have attracted increasing attention in organic synthesis, leading to improvement existing reactions, as well the discovery unprecedented transformations. Thus, photochemical or photocatalytic generation both carbenes and radicals provide milder tools toward these key intermediates for many valuable However, vast majority transformations represent new reactivity modes compounds, which are achieved by decomposition photoredox catalysis. particular, use a redox-active photocatalysts opens avenue plethora radical reactions. The application methods led inaccessible classical associated with metal carbenes. most cases, act sources but can also serve acceptors. Importantly, described processes operate under mild, practical conditions. This Review describes this subfield compound chemistry, particularly focusing on advancements.

Язык: Английский

---

Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Сен. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Язык: Английский

---

Reactivity of α-diazo sulfonium salts: rhodium-catalysed ring expansion of indenes to naphthalenes

Chemical Science, Год журнала: 2024, Номер 15(16), С. 5938 - 5943

Опубликована: Янв. 1, 2024

Cyclopropyl-substituted sulfonium salts are obtained by Rh-catalysed addition of α-diazo dibenzothiophenium to olefins. When indenes used as substrates, initially formed cyclopropyl rings open with concomitant elimination dibenzothiophene, enabling access 2-substituted naphthalenes.

Язык: Английский

---

Trifluoromethyl Rhodium‐Carbynoid in [2+1+2] Cycloadditions

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(13)

Опубликована: Янв. 18, 2024

Abstract Trifluoromethyl cationic carbyne (CF 3 C + :) possessing dual carbene‐carbocation behavior emulated as trifluoromethyl metal‐carbynoid =M) has not been explored yet, and its reaction characteristics are unknown. Herein, a novel α‐diazotrifluoroethyl sulfonium salt was prepared used in Rh‐catalyzed three‐component [2+1+2] cycloadditions for the first time with commercially available N ‐fused heteroarenes nitriles, yielding series of imidazo[1,5‐ ] ‐heterocycles that interest medicinal chemistry, which insertion Rh‐carbynoid =Rh) into C=N bonds involved. This strategy demonstrates synthetic applications late‐stage modification pharmaceuticals, construction CD ‐containing ‐heterocycles, gram‐scale experiments, synthesis phosphodiesterase 10A inhibitor analog. These highly valuable modifiable exhibit good antitumor activity vitro, thus demonstrating their potential chemistry.

Язык: Английский

---

Dibenzothiophenium Salts: Practical Alternatives to Hypervalent I(III)-Based Reagents

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

Опубликована: Фев. 2, 2025

ConspectusDuring the past few years, interest among organic synthesis practitioners in use of sulfonium salts has exponentially growth. This can arguably be attributed to a series specific factors: (a) The recent development more direct and efficient protocols for these species, which make reagents wide structural variety easily available multigram scale. (b) recognition that reactivity resembles hypervalent iodine compounds, therefore, they used as effective replacement such species most their applications. (c) Their intrinsic thermal stability tolerance air moisture, clearly surpass I(III)-reagents analogue reactivity, facilitate purification, isolation well-defined storage, safely handling on larger (d) Finally, possibility further functionalize once sulfur-containing platform been incorporated. Specifically, this last synthetic approach is not trivial when working with I(III)-species facilitates access no counterpart I(III) realm.This renewed led improvement already existing transformations well discovery unprecedented ones; particular, by incorporate partners traditional cross-coupling C–H activation steps or combine them modern technologies photocatalysis electrosynthesis. In Account, originally prepared our laboratory will outlined compared I(III)-counterparts. Some are now commercially available, started spread widely across chemistry community, helping speed process identification potentially bioactive products new functionaliced materials. However, challenges still remain. characterized an optimal balance between site-selectivity, showing broader compatibility toward sensitive functional groups need. addition, often makes necessary (sophisticated) catalysts activate latent hidden structures. Although priori one see fact disadvantage, it might actually decisive harvest full potential because surely preparation operational context I(III)-chemistry. If becomes true, may contribute expediting retrosynthetic disconnections that, date, impossible.

Язык: Английский

---

Multiprobe Photoproximity Labeling of the EGFR Interactome in Glioblastoma Using Red-Light

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Photocatalytic proximity labeling has emerged as a valuable technique for studying interactions between biomolecules in cellular context, providing precise spatiotemporal control over protein labeling. One significant advantage of these methods is their modularity, allowing the use single photocatalyst with different reactive probes to expand interactome coverage and capture diverse interactions. Despite advances, fewer have been developed using red-light excitation, limiting photoproximity more complex media such tissues animal models. Herein, we develop platform under utilizing catalyst two distinct probe types. We first design carbene based system that utilizes sulfonium diazo probes. This successfully applied on A549 cells epidermal growth factor receptor (EGFR) Cetuximab-Chlorin e6 conjugate. Benchmarking against established techniques indicates this approach performs comparably leading carbene-based methods. Next, leverage strong singlet oxygen generation (SOG) ability Chlorin establish an alternative aniline hydrazide EGFR directed chemoproteomics experiments reveal overlap system, capturing subset identified by SOG system. Finally, deploy our characterization resected human glioblastoma (GBM) tissue samples removed from locations same tumor, representing tumor's infiltrating edge its viable center, identifying several GBM specific interacting proteins may serve launch point future therapeutic campaigns.

Язык: Английский

---

Electron Donor–Acceptor Complex Enabled Radical Cyclization of α-Diazodifluoroethyl Sulfonium Salt with Unactivated Alkynes

Organic Letters, Год журнала: 2023, Номер 25(50), С. 9041 - 9046

Опубликована: Дек. 13, 2023

An α-diazodifluoroethane sulfonium reagent was developed in this study to undergo [3 + 2] radical cyclization with unactivated alkynes give the corresponding 3-difluoromethyl pyrazoles under blue light irradiation conditions. The key success of transformation lies formation an electron donor-acceptor (EDA) complex between electron-deficient α-diazo salt and electron-rich triaryl amine. This circumvents a major substrate scope limitation polar cycloaddition reactions existent diazodifluoroethane reagents.

Язык: Английский

---

α-(N-Alkyl-N-heteroarenium)-α-diazoacetates: synthesis and reactivity of a novel class of ‘onium’ diazo compounds

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Unprecedented diazoacetate N -heteroarenium salts are synthesized and participate in catalytic [2 + 1] cycloadditions [2,3]-sigmatropic rearrangements, providing facile access to otherwise difficult-to-obtain multi-functionalized -heterocycles.

Язык: Английский

---

Diazomethyl-λ³-iodane meets aryne: Dipolar cycloaddition and C-to-N iodane shift leading to indazolyl-λ³-iodanes

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Diazomethyl-λ 3 -iodanes have recently emerged as carbyne equivalents in organic synthesis, enabling the construction of multi-substituted carbon centers through strategic sequential activation diazo and iodane functional groups. Distinct from...

Язык: Английский

---

Photoinduced [3 + 2] Radical Cyclization of α-Diazodifluoroethyl Sulfonium Salt with Hydrazones

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 12, 2025

Here we report a photoinduced [3 + 2] radical cyclization reaction of α-diazodifluoroethane sulfonium reagent with hydrazones to give the corresponding N-amino-4-difluoromethyl-1,2,3-triazoles. This transformation proceeds under simple blue light irradiation conditions without need photocatalyst. Preliminary mechanistic studies indicate that formation an electron donor-acceptor (EDA) complex between electron-deficient α-diazo triflate and electron-rich hydrazone operates as key mediator.

Язык: Английский

---