Photochemical C–H Borylation in Organic Synthesis DOI Creative Commons
Supriya Rej, Stephanie G. E. Amos, Arjan W. Kleij

и другие.

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1753 - 1770

Опубликована: Янв. 16, 2025

Although C–H bond functionalization has been extensively studied since its discovery in 1955, the borylation of organic compounds by activating bonds only became popular valuable Hartwig 1995 who considered a wider application these transformations synthetic chemistry. For borylation, catalytic activation this generally low-reactivity can be performed many ways. Among approaches reported are use and stoichiometric reagents, thermal activation, photochemical suitable substrates. Iridium-, ruthenium-, rhodium-based protocols using have played crucial role toward establishment area. Photochemical though, scarcely explored despite fact that it represents comparably environmentally benign protocol light as renewable energy source. In literature survey, we highlight recent developments from initial inception up to latest advancements.

Язык: Английский

C–H Bond Functionalization of Amines: A Graphical Overview of Diverse Methods DOI Creative Commons

Subhradeep Dutta,

Bowen Li,

Dillon R. L. Rickertsen

и другие.

SynOpen, Год журнала: 2021, Номер 05(03), С. 173 - 228

Опубликована: Июль 1, 2021

This Graphical Review provides a concise overview of the manifold and mechanistically diverse methods that enable functionalization sp

Язык: Английский

Процитировано

65
Remote C(sp3)−H Acylation of Amides and Cascade Cyclization via N‐Heterocyclic Carbene Organocatalysis DOI
Qing‐Zhu Li, Rong Zeng, Fan Yang

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(15)

Опубликована: Фев. 3, 2022

Abstract The direct functionalization of inert C(sp 3 )−H bonds under environmentally benign catalytic conditions remains a challenging task in synthetic chemistry. Here, we report an organocatalytic remote acylation amides and cascade cyclization through radical‐mediated 1,5‐hydrogen atom transfer mechanism using N‐heterocyclic carbene as the catalyst. Notably, diversity nitrogen‐containing substrates, including simple linear aliphatic carbamates ortho ‐alkyl benzamides, can be successfully applied to this system. With established protocol, over 120 examples functionalized δ‐amino ketones isoquinolinones with diverse substituents were easily synthesized up 99 % yield mild conditions. robustness generality strategy further highlighted by successful unactivated late‐stage modification pharmaceutical molecules. Then, asymmetric control radical reaction was attempted proven feasible newly designed chiral thiazolium catalyst, moderate enantioselectivity obtained at current stage. Preliminary mechanistic investigations several reactions, KIE experiments, computational studies shed light on mechanism.

Язык: Английский

Процитировано

65
Deciphering the Role of Silver in Palladium-Catalyzed C–H Functionalizations DOI
Trisha Bhattacharya, Subhabrata Dutta, Debabrata Maiti

и другие.

ACS Catalysis, Год журнала: 2021, Номер 11(15), С. 9702 - 9714

Опубликована: Июль 19, 2021

Over the years, silver salts have become an integral part of palladium-catalyzed C–H functionalization. Although most research works highlight role Ag(I) complexes solely as oxidant, there are several other impacts such in Pd-catalyzed functionalizations. The low energy route adopted by this bimetallic couple reportedly outshines pre-existing monometallic catalysis. Extensive computational studies further corroborates fact electronic relay between two metal species. This perspective aims to eradicate vague intuition merely acting oxidant unveiling different aspects Ag activation.

Язык: Английский

Процитировано

62
Three-component carboacylation of alkenes via cooperative nickelaphotoredox catalysis DOI Creative Commons
Dingyi Wang, Lutz Ackermann

Chemical Science, Год журнала: 2022, Номер 13(24), С. 7256 - 7263

Опубликована: Янв. 1, 2022

Various commercially available acyl chlorides, aldehydes, and alkanes were exploited for versatile three-component 1,2-carboacylations of alkenes to forge two vicinal C-C bonds through the cooperative action nickel sodium decatungstate catalysis. A wealth ketones with high levels structural complexity was rapidly obtained via direct functionalization C(sp2)/C(sp3)-H in a modular manner. Furthermore, regioselective late-stage modification natural products showcased practical utility strategy, generally featuring resource economy ample substrate scope.

Язык: Английский

Процитировано

52
Visible light metallaphotoredox catalysis in the late-stage functionalization of pharmaceutically potent compounds DOI
Praveen P. Singh, Pravin K. Singh, Vishal Srivastava

и другие.

Organic Chemistry Frontiers, Год журнала: 2022, Номер 10(1), С. 216 - 236

Опубликована: Ноя. 8, 2022

The late stage functionalization (LSF) is a distinctive approach for accelerating the discovery of structure–activity relationships (SARs) and optimising ADME (absorption, distribution, metabolism, excretion) profiles.

Язык: Английский

Процитировано

44
The green chemistry paradigm in modern organic synthesis DOI
Sergei G. Zlotin, Ksenia S. Egorova, Valentine P. Ananikov

и другие.

Russian Chemical Reviews, Год журнала: 2023, Номер 92(12), С. RCR5104 - RCR5104

Опубликована: Дек. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Язык: Английский

Процитировано

41
Sulfoxide-Directed or 3d-Metal Catalyzed C–H Activation and Hypervalent Iodines as Tools for Atroposelective Synthesis DOI

Sabine Choppin,

Joanna Wencel‐Delord

Accounts of Chemical Research, Год журнала: 2023, Номер 56(3), С. 189 - 202

Опубликована: Янв. 27, 2023

ConspectusThe expanding applications of atropisomeric compounds combined with the growing diversity such chiral molecules translate into an urgent need for innovative synthetic strategies allowing their rapid, efficient, and sustainable synthesis. Recently, C-H activation approach has provided new opportunities synthesizing axially compounds. The two complementary approaches implementation methodology toward synthesis imply either ortho-functionalization preexisting prochiral or atropo-unstable biaryl substrates direct arylation sterically encumbered aromatics. first required preinstallation a directing group on precursor, which drastically limits thus generated products. To tackle this important limitation, we have envisioned using sulfoxide as both auxiliary. Indeed, in addition to efficiently coordinating Pd-catalyst induction, moiety can be easily removed, via sulfoxide/lithium exchange, after step, guaranteeing almost unlimited postdiversification efficiency generality concept could illustrated by developing atropo-diastereoselective oxidative Heck reaction, acetoxylation, iodination, well arylation. Besides, utility was demonstrated designing expedient steganone precursor. This unique transformation also allowed us build up unprecedented triaryl scaffolds perfectly controlled axes, original skeletons ligand design. While considering atroposelective arylations, clear antagonism between harsh reaction conditions frequently coupling hindered atropo-stability product, resulted scarcity transformations. solve fundamental challenge, focused application low-valent cobalt catalyst, prompted catalyze indoles at C2 position under extremely mild (room temperature). Accordingly, C2-arylation achieved carbene delivering uncommon atropoisomerically pure excellent yields enantioselectivities. Detailed experimental theoretical mechanistic studies shed light mechanism transformation, providing strong evidence regarding origin enantioselectivity. Finally, steric hindrance guarantee molecule couple partners is limitation not only development but C-N Despite long history incredible advances Ullmann-Goldberg Buchwald-Hartwig couplings, versions transformations remained until recently. Our idea challenging issue consisted hypervalent iodines highly reactive partners, desired N-arylations occur room temperature. hypothesis validated reporting Cu-catalyzed N-arylation, λ3-iodanes partners. Subsequently, enantioselective version N-arylation successfully established Cu-complex bearing BOX ligand. In conclusion, report herein tailored-made solutions provide construct molecules, including biaryls molecules.

Язык: Английский

Процитировано

30
Room temperature photo-promoted iron-catalysed arene C–H alkenylation without Grignard reagents DOI
Antonis M. Messinis, Tristan von Münchow, Max Surke

и другие.

Nature Catalysis, Год журнала: 2024, Номер 7(3), С. 273 - 284

Опубликована: Фев. 13, 2024

Язык: Английский

Процитировано

13
Enantioselective Cobaltaphotoredox-Catalyzed C–H Activation DOI Creative Commons
Yang Xu, Lin Ye, Simon L. Homölle

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(34), С. 24105 - 24113

Опубликована: Авг. 15, 2024

The quest for sustainable strategies in molecular synthesis has spurred the emergence of photocatalysis as a particularly powerful technique. In recent years, application this context greatly promoted development asymmetric catalysis. Despite impressive advances, enantioselective photoinduced strong arene C-H activations by cobalt catalysis remain unexplored. Herein, we report strategy that merges organic photoredox and cobalt-catalyzed activation, enabling regio- stereoselective dual functionalization indoles an fashion. Thereby, assembly various chiral indolo[2,3-

Язык: Английский

Процитировано

10
Metal- and additive-free C–H oxygenation of alkylarenes by visible-light photoredox catalysis DOI

Mustafa Uygur,

Jan Kuhlmann,

María Carmen Pérez-Aguilar

и другие.

Green Chemistry, Год журнала: 2021, Номер 23(9), С. 3392 - 3399

Опубликована: Янв. 1, 2021

A metal- and additive-free methodology for the highly selective, photocatalyzed C–H oxygenation of alkylarenes under air to corresponding carbonyls is presented.

Язык: Английский

Процитировано

53