3d Transition Metals for C–H Activation

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2192 - 2452

Published: Nov. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Language: Английский

---

Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly Enantioselective 3d-Metal-Catalyzed C–H Functionalizations

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(14), P. 5675 - 5680

Published: March 22, 2019

The synthesis of a set cobalt(III)-complexes equipped with trisubstituted chiral cyclopentadienyl ligands is reported, and their steric electronic parameters are mapped. application potential these complexes for asymmetric C-H functionalizations 3d-metals shown by the dihydroisoquinolones from N-chlorobenzamides broad range alkenes. transformation proceeds excellent enantioselectivities up to 99.5:0.5 er high regioselectivities. observed values outperform best rhodium(III)-based methods this reaction type. Moreover, challenging substrates such as alkyl alkenes also react regio- enantioselectivities.

Language: Английский

---

Weak-Coordination in C–H Bond Functionalizations Catalyzed by 3d Metals

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(6), P. 3452 - 3506

Published: March 3, 2022

Transition-metal-catalyzed C–H bond functionalizations have had an enormous influence on organic synthesis in recent times. However, the use of low-abundance 4d and 5d metals is almost inevitable, they are high demand. This will be a cause concern, hence, it important to develop methods based 3d metals, which widely present Earth's crust. In this regard, metal catalysts or their precursors for catalysis, general, functionalizations, particular, has gained significant momentum The major development catalytic with been achieved predominantly strongly coordinating directing groups such as pyridyl, pyrimidinyl, pyrazolyl, 8-amino-quinolinyl groups. Thus, prefunctionalization substrates these necessary, contradicts step- atom-economy activation. commonly available functional aldehyde, ketone, carboxylic acid, amide, hydroxy, N-oxides loosely bind through weak-coordination. These weakly orient activate regioselectively without need preinstalled Although challenging, contemporary topic actively pursued by many researchers Through article, we provide comprehensive overview metal-catalyzed, coordinating, directing-group-enabled reported until March 2021.

Language: Английский

---

Cobalt‐Catalyzed Annulation Reactions via C−H Bond Activation

ChemCatChem, Journal Year: 2017, Volume and Issue: 10(4), P. 683 - 705

Published: Nov. 1, 2017

Abstract Considerable research attention has been directed towards the use of first‐row transition metals in organic synthesis. The more abundant, and less expensive cobalt is considered to be an effective alternative for second third‐row noble metals, especially C−H bond functionalization reactions. In this Minireview, we will summarize features, recent achievements Co‐catalyzed directing group assisted activation/cyclization reactions their mechanistic insights.

Language: Английский

---

Cp*M-Catalyzed Direct Annulation with Terminal Alkynes and Their Surrogates for the Construction of Multi-Ring Systems

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(17), P. 9747 - 9757

Published: Aug. 3, 2020

Transition-metal-catalyzed C–H activation followed by oxidative cyclization with unsaturated coupling partners has been a valuable synthetic tool for the multiring molecular scaffolds. This Perspective introduces recent progress on Cp*M-catalyzed (M = Co, Rh, and Ir) direct annulation of functionalized arenes terminal alkynes their equivalents through bond cleavage. The highlighted examples are categorized according to 10 different types reagents used in transformations. representative conditions, selected reaction scope, key mechanistic aspects briefly summarized.

Language: Английский

---

Electrifying green synthesis: recent advances in electrochemical annulation reactions

Green Chemistry, Journal Year: 2020, Volume and Issue: 22(15), P. 4849 - 4870

Published: Jan. 1, 2020

Herein, electrochemical annulations involving mediators and mediator-free conditions have been discussed. Also, the use of sacrificial electrodes has explored.

Language: Английский

---

C−H Bond Activation for the Synthesis of Heterocyclic Atropisomers Yields Hedgehog Pathway Inhibitors

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(43), P. 14250 - 14254

Published: Sept. 11, 2018

Abstract Axially chiral 4‐arylisoquinolones are endowed with pronounced bioactivity, and methods for their efficient synthesis have gained widespread attention. However, enantioselective of axially by means C−H activation has not been reported to date. Described here is a rhodium (III)‐catalyzed bond annulation the atroposelective 4‐arylisoquinolones. The method employs cyclopentadienyl ligands embodying piperidine ring as backbone yields atropisomers good excellent enantioselectivity. Biological relevance was demonstrated investigation in different cellular assays, leading discovery novel non‐SMO (SMO= smoothened) binding Hedgehog pathway inhibitors.

Language: Английский

---

C–H bond functionalization by high-valent cobalt catalysis: current progress, challenges and future perspectives

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(83), P. 10827 - 10841

Published: Jan. 1, 2021

Over the last decade, high-valent cobalt catalysis has earned a place in spotlight as valuable tool for C-H activation and functionalization. Since discovery of its unique reactivity, more attention been directed towards utilization an alternative to noble metal catalysts. In particular, Cp*Co(III) complexes, well simple Co(II) Co(III) salts combination with bidentate chelation assistance, have extensively used development novel transformations. this review, we demonstrated existing trends functionalization methodology using highlighted main challenges overcome, perspective directions, which need be further developed future.

Language: Английский

---

Cobalt(III)-Catalyzed [4 + 2] Annulation of N-Chlorobenzamides with Maleimides

Organic Letters, Journal Year: 2019, Volume and Issue: 21(4), P. 1068 - 1072

Published: Jan. 28, 2019

A Co(III)-catalyzed novel [4 + 2] annulation of N-chlorobenzamides with maleimides has been reported. Mostly, are known to furnish the Michael-type or 1,1-type cyclized products while treating amides. In this reaction, furnished annulated in good yields at room temperature being treated internal oxidizing N-chlorobenzamide as a directing group. The developed methodology is compatible variety functional groups. obtained featured some biologically active molecules.

Language: Английский

---

Electrochemically Enabled Double C–H Activation of Amides: Chemoselective Synthesis of Polycyclic Isoquinolinones

Organic Letters, Journal Year: 2019, Volume and Issue: 21(24), P. 9841 - 9845

Published: Dec. 12, 2019

We developed an electrochemically enabled dehydrogenative annulation reaction of amides and alkynes for the synthesis antitumor polycyclic isoquinolinones through a double C-H activation route. No external oxidant is required in this reaction, electricity used Ru catalyst circulation. The most remarkable feature effective improvement product regioselectivity under mild electrolytic conditions comparison with previously set strong conditions.

Language: Английский

---