Cobaltaelectro‐Catalyzed C–H Activation for Central and Axial Double Enantio‐Induction DOI Creative Commons
Tristan von Münchow, Yi‐Ru Liu, Rahul Parmar

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 17, 2024

Abstract In den letzten Jahren hat sich die enantioselektive Elektrokatalyse zunehmend als eine effektive Methode für nachhaltige molekulare Synthese herausgestellt. Trotz unbestreitbarer Fortschritte bleiben Strategien zur Kontrolle über zwei unterschiedliche stereogene Elemente mit hoher Selektivität schwer fassbar. Im Gegensatz dazu beschreiben wir hier elektrochemische Cobalt‐katalysierte C−H‐Aktivierungen, welche Installation chiraler stereogener Zentren zusammen einer chiralen Achse Enantio‐ und Diastereoselektivität ermöglichen. Die entwickelte elektrokatalytische Strategie erlaubte C−H/N−H‐Aktivierungen/Anellierungen cyclischen acyclischen Alkenen gewährte einen direkten Zugang zu vielseitigen sowohl zentralen auch atropo‐chiralen Dihydroisochinolinonen gepaart der wertvollen Wasserstoffbildungsreaktion. Studien Atropo‐Stabilität erhaltenen Verbindungen demonstrierten, dass äußerst milden Bedingungen, gewährleistet durch elektrokatalytischen Prozess, entscheidend hohen erzielten Stereoselektivitäten waren.

Enantioselective synthesis of molecules with multiple stereogenic elements DOI Creative Commons
Arthur Gaucherand, Expédite Yen‐Pon,

Antoine Domain

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(22), P. 11165 - 11206

Published: Jan. 1, 2024

This review explores the fascinating world of molecules featuring multiple stereogenic elements, unraveling different strategies designed over years for their enantioselective synthesis.

Language: Английский

Citations

17
Cobaltaelectro‐Catalyzed C–H Activation for Central and Axial Double Enantio‐Induction DOI Creative Commons
Tristan von Münchow, Yi‐Ru Liu, Rahul Parmar

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 17, 2024

In recent years, enantioselective electrocatalysis has surfaced as an increasingly-effective platform for sustainable molecular synthesis. Despite indisputable progress, strategies that allow the control of two distinct stereogenic elements with high selectivity remain elusive. contrast, we, herein, describe electrochemical cobalt-catalyzed C-H activations enable installation chiral centers along a axis levels enantio- and diastereoselectivities. The developed strategy allowed C-H/N-H activations/annulations cyclic non-cyclic alkenes providing expedient access to various central well atropo-chiral dihydroisoquinolinones paired valuable hydrogen evolution reaction. Studies on atropo-stability obtained compounds demonstrated exceedingly mild conditions ensured by electrocatalytic process were key achieved stereoselectivities.

Language: Английский

Citations

11
Dual Catalytic C(sp2)–H Activation of Azaheterocycles toward C–N Atropisomers DOI
Juntao Sun, Yiyao Hu, Wen‐Ji He

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3700 - 3710

Published: Feb. 14, 2025

Language: Английский

Citations

1
Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp3)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development DOI
Weijie Chen, Huiying Xu,

Fu‐Xiaomin Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 19, 2024

Abstract Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp 3 )−H functionalization, among which Os(II)/Salox species is found be most efficient for precise stereocontrol in realizing amidation. As exemplified by enantioenriched pyrrolidinone synthesis, such tailored catalyst efficiently enables an intramolecular site‐/enantioselective amidation γ‐position dioxazolone substrates, benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording corresponding γ‐lactam products with good er values (up 99 : 1) diverse functionality (>35 examples). The unique performance advantage developed system terms catalytic energy profile induction has further clarified integrated experimental computational studies.

Language: Английский

Citations

3
Asymmetric 1,2-diaxial synthesis of bi-(hetero)aryl benzofulvene atropisomers via transient directing group-assisted dehydrogenative coupling DOI
Soumyadip Hore, Abhijeet Singh, Ravi P. Singh

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(18), P. 2524 - 2527

Published: Jan. 1, 2024

The efficient cross-dehydrogenative coupling of electronically rich and sterically congested benzofulvene with bi-(hetero)aryl moieties to construct an axially chiral core remains a formidable task.

Language: Английский

Citations

1
Iridium-Catalyzed Asymmetric Hydroarylation of Unactivated Alkenes with Heterobiaryls: Simultaneous Construction of Axial and Central Chirality DOI
Fei Li, Yicong Luo,

Jinbao Ren

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(32), P. 6835 - 6840

Published: Aug. 7, 2024

There are only a few examples being reported for the simultaneous control of central chirality and axial because it is more challenging. Herein, we report an iridium-catalyzed asymmetric hydroarylation unactivated alkenes with heterobiaryls to simultaneously construct chirality. The reaction showed broad substrate scope delivered products satisfactory results. results experiments demonstrated that FerroLANE ligand promotes proceed along specific modified Chalk-Harrod mechanism.

Language: Английский

Citations

1
Diastereodivergent Parallel Kinetic Resolution of Racemic 2-Substituted Pyrrolidines via Iridium-Catalyzed C(sp3)–H Borylation DOI
Maosheng He, Liangjun Xie, Lili Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 18701 - 18707

Published: Dec. 8, 2024

Chiral 2,5-disubstituted pyrrolidines are ubiquitous subunits in natural products, bioactive compounds, pharmaceuticals, and chiral catalysts. However, their asymmetric synthesis still presents a formidable challenge. We herein report rare example of diastereodivergent parallel kinetic resolution racemic 2-substituted via C(sp3)–H borylation. A vast array enantioenriched cis- trans-2,5-disubstituted were obtained with high enantioselectivities. The synthetic utility was demonstrated by downstream transformations, including the optically active pyrrolidine 197B cis-pyrrolidine 225H.

Language: Английский

Citations

1
Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp3)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development DOI
Weijie Chen, Huiying Xu,

Fu‐Xiaomin Liu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(20)

Published: March 19, 2024

Abstract Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp 3 )−H functionalization, among which Os(II)/Salox species is found be most efficient for precise stereocontrol in realizing amidation. As exemplified by enantioenriched pyrrolidinone synthesis, such tailored catalyst efficiently enables an intramolecular site‐/enantioselective amidation γ‐position dioxazolone substrates, benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording corresponding γ‐lactam products with good er values (up 99 : 1) diverse functionality (>35 examples). The unique performance advantage developed system terms catalytic energy profile induction has further clarified integrated experimental computational studies.

Language: Английский

Citations

0
Cobaltaelectro‐Catalyzed C–H Activation for Central and Axial Double Enantio‐Induction DOI Creative Commons
Tristan von Münchow, Yi‐Ru Liu, Rahul Parmar

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 17, 2024

Abstract In den letzten Jahren hat sich die enantioselektive Elektrokatalyse zunehmend als eine effektive Methode für nachhaltige molekulare Synthese herausgestellt. Trotz unbestreitbarer Fortschritte bleiben Strategien zur Kontrolle über zwei unterschiedliche stereogene Elemente mit hoher Selektivität schwer fassbar. Im Gegensatz dazu beschreiben wir hier elektrochemische Cobalt‐katalysierte C−H‐Aktivierungen, welche Installation chiraler stereogener Zentren zusammen einer chiralen Achse Enantio‐ und Diastereoselektivität ermöglichen. Die entwickelte elektrokatalytische Strategie erlaubte C−H/N−H‐Aktivierungen/Anellierungen cyclischen acyclischen Alkenen gewährte einen direkten Zugang zu vielseitigen sowohl zentralen auch atropo‐chiralen Dihydroisochinolinonen gepaart der wertvollen Wasserstoffbildungsreaktion. Studien Atropo‐Stabilität erhaltenen Verbindungen demonstrierten, dass äußerst milden Bedingungen, gewährleistet durch elektrokatalytischen Prozess, entscheidend hohen erzielten Stereoselektivitäten waren.

Citations

0