Tetrahedron Chem, Год журнала: 2024, Номер 9, С. 100068 - 100068
Опубликована: Фев. 24, 2024
Язык: Английский
Journal of the American Chemical Society, Год журнала: 2024, Номер unknown
Опубликована: Сен. 25, 2024
The selective construction of bridged bicyclic scaffolds has garnered increasing attention because their extensive use as saturated bioisosteres arene in pharmaceutical industry. However, sharp contrast to racemic counterparts, assembling chiral structures an enantioselective and regioselective manner remains challenging. Herein, we describe our protocol for constructing 2-oxa-3-azabicyclo[3.1.1]heptanes (BCHeps) by [4π + 2σ] cycloadditions bicyclo[1.1.0]butanes (BCBs) nitrones taking advantage a copper(II) complex Lewis acid catalyst. This method features mild conditions, good functional group tolerance, high yield (up 99%), excellent enantioselectivity 99% ee). Density theory (DFT) calculation elucidates the origin reaction's mechanism BCB activation Cu(II) complex.
Язык: Английский
Процитировано
17
Journal of the American Chemical Society, Год журнала: 2023, Номер 145(49), С. 26774 - 26782
Опубликована: Ноя. 29, 2023
Direct decarboxylative alkenylation of widely available aliphatic carboxylic acids with vinyl halides for the synthesis alkenes all substitution patterns has been accomplished by means Ce/Ni dual transition metal electrocatalysis. The reactions employ alkyl as limiting reagents and exhibit a broad scope respect to both coupling partners. Notably, simple primary could be readily engaged carbon-centered radical precursors in reaction. This new protocol successfully demonstrated direct modification naturally occurring complex is amenable enantioselective arylacetic acid. Mechanistic studies, including series controlled experiments cyclic voltammetry data, allow us probe key intermediates pathway
Язык: Английский
Процитировано
29
Science, Год журнала: 2024, Номер 385(6715), С. 1331 - 1337
Опубликована: Сен. 19, 2024
The myriad nickel-catalyzed cross-coupling reactions rely on the formation of an organonickel intermediate, but limitations in forming monoalkylnickel species have limited options for C(sp 3 ) cross-coupling. monoalkylnickel(II) from abundant carboxylic acid esters would be valuable, derivatives are primarily decarboxylated to form alkyl radicals that lack correct reactivity. In this work, we disclose a facile oxidative addition and decarbonylation sequence forms intermediates through nonradical process. key ligand, bis(4-methylpyrazole)pyridine, accelerates decarbonylation, stabilizes alkylnickel(II) destabilizes off-cycle nickel(0) carbonyl species. utility new reactivity )-C(sp bond is demonstrated reaction challenging by purely radical methods—the selective primary with iodides.
Язык: Английский
Процитировано
12
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(34), С. 24042 - 24052
Опубликована: Авг. 13, 2024
Alkyl organoborons are powerful materials for the construction of C(
Язык: Английский
Процитировано
9
Organic Letters, Год журнала: 2024, Номер 26(15), С. 3174 - 3178
Опубликована: Апрель 8, 2024
A concept for the dual use of acridine and tetrabutylammonium decatungstate photocatalysts in reactions carboxylic acids is proposed. Imines generated situ from aldehydes p-methoxyaniline, as well other azomethines, were used radical acceptors. The role believed to facilitate turnover photocatalyst by means hydrogen atom transfer.
Язык: Английский
Процитировано
8
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)
Опубликована: Май 13, 2024
Abstract We report an iron‐catalyzed decarboxylative C(sp 3 )−O bond‐forming reaction under mild, base‐free conditions with visible light irradiation. The transformation uses readily available and structurally diverse carboxylic acids, iron photocatalyst, 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) derivatives as oxygenation reagents. process exhibits a broad scope in acids possessing wide range of stereoelectronic properties functional groups. developed was applied to late‐stage series bio‐active molecules. leverages the ability complexes generate carbon‐centered radicals directly from by photoinduced carboxylate‐to‐iron charge transfer. Kinetic, electrochemical, EPR, UV/Vis, HRMS, DFT studies revealed that TEMPO has triple role reaction: reagent, oxidant turn over Fe‐catalyst, internal base for acid deprotonation. obtained adducts represent versatile synthetic intermediates were further engaged C−C C‐heteroatom reactions using commercial organo‐photocatalysts nucleophilic
Язык: Английский
Процитировано
7
ChemCatChem, Год журнала: 2024, Номер 16(14)
Опубликована: Янв. 5, 2024
Abstract In the past century, significant advancements in synthetic chemistry undeniably contributed to wellness of mankind, from development new drugs design materials for energy production and storage. However, this technological progress has also brought forth challenges, emphasizing urgent need rethink more environmentally friendly approaches. Review a critical comprehensive analysis sustainability preparation commonly used photocatalysts is performed, by employing mass‐based metrics. Additionally, comparative evaluation made between some selected photocatalytic protocols traditional reactions not relying on light. The objective quantitatively evaluate claims greenness associated with photocatalysis, exploring real impact procedures waste generation. This quantitative approach provides insights into broader concept sustainable processes, challenging assumptions encouraging rigorous green catalysis. Furthermore, toxicity involved species availability required chemical elements commented provide global perspective analyzed transformations. results shed light true environmental footprint photocatalysis reveal that notion can sometimes be overstated.
Язык: Английский
Процитировано
6
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)
Опубликована: Май 24, 2024
Controlling the cross-coupling reaction between two different radicals is a long-standing challenge due to process occurring statistically, which would lead three products, including homocoupling products and one product. Generally, selectivity achieved by persistent radical effect (PRE) that requires presence of transient radical, thus resulting in limited precursors. In this paper, highly selective alkyl with acyl construct C(sp
Язык: Английский
Процитировано
6
Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(33), С. 6650 - 6664
Опубликована: Янв. 1, 2024
Titanium, as an important transition metal, has garnered extensive attention in both industry and academia due to its excellent mechanical properties, corrosion resistance, unique reactivity organic synthesis. In the field of photocatalysis, titanium-based compounds such titanium dioxide (TiO
Язык: Английский
Процитировано
6
Chemical Science, Год журнала: 2023, Номер 14(36), С. 9806 - 9813
Опубликована: Янв. 1, 2023
A direct intermolecular decarboxylative Giese amidation reaction from bench stable, non-toxic and environmentally benign oxamic acids has been developed, which allows for easy access to 1,4-difunctionalised compounds are not otherwise readily accessible. Crucially, a more general acceptor substrate scope is now possible, renders the applicable complex substrates such as natural products chiral building blocks. Two different photocatalytic methods (one via oxidative other reductive quenching cycles) one metal- light-free method were developed flexibility provided by conditions proved be crucial enabling scope.
Язык: Английский
Процитировано
14