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

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(34), P. 24105 - 24113

Published: Aug. 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-

Language: Английский

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

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(15)

Published: Feb. 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.

Language: Английский

Citations

65
Evolution of BODIPY/aza-BODIPY dyes for organic photoredox/energy transfer catalysis DOI

Priksha Rana,

Nishi Singh, Poulomi Majumdar

et al.

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 470, P. 214698 - 214698

Published: July 8, 2022

Language: Английский

Citations

63
Deciphering the Role of Silver in Palladium-Catalyzed C–H Functionalizations DOI
Trisha Bhattacharya, Subhabrata Dutta, Debabrata Maiti

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(15), P. 9702 - 9714

Published: July 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.

Language: Английский

Citations

60
Three-component carboacylation of alkenes via cooperative nickelaphotoredox catalysis DOI Creative Commons
Dingyi Wang, Lutz Ackermann

Chemical Science, Journal Year: 2022, Volume and Issue: 13(24), P. 7256 - 7263

Published: Jan. 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.

Language: Английский

Citations

51
Visible light metallaphotoredox catalysis in the late-stage functionalization of pharmaceutically potent compounds DOI
Praveen P. Singh, Pravin K. Singh, Vishal Srivastava

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 10(1), P. 216 - 236

Published: Nov. 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.

Language: Английский

Citations

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

et al.

Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104

Published: Dec. 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.

Language: Английский

Citations

39
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, Journal Year: 2023, Volume and Issue: 56(3), P. 189 - 202

Published: Jan. 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.

Language: Английский

Citations

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

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(3), P. 273 - 284

Published: Feb. 13, 2024

Language: Английский

Citations

11
Metal- and additive-free C–H oxygenation of alkylarenes by visible-light photoredox catalysis DOI

Mustafa Uygur,

Jan Kuhlmann,

María Carmen Pérez-Aguilar

et al.

Green Chemistry, Journal Year: 2021, Volume and Issue: 23(9), P. 3392 - 3399

Published: Jan. 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.

Language: Английский

Citations

49
Advances in allylic and benzylic C–H bond functionalization enabled by metallaphotoredox catalysis DOI Creative Commons
Huifeng Yue, Chen Zhu, Long Huang

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 58(2), P. 171 - 184

Published: Dec. 6, 2021

Metallaphoto-catalysis has been established as a robust platform for efficient construction of range chemical bonds. Moreover, transformation native functionalities such C(sp3)-H bonds to produce functional molecules represents one the most attractive strategies in organic synthesis. Merging two powerful methodologies, metallaphoto-catalyzed benzylic and allylic bond functionalizations provide series general mild approaches diversification alkylbenzenes alkenes.

Language: Английский

Citations

45