Cobalt-Catalyzed Enantioselective C–H Annulation of Benzylamines with Alkynes: Application to the Modular and Asymmetric Syntheses of Bioactive Molecules DOI

Yong‐Jie Wu,

Jiahao Chen,

Ming‐Ya Teng

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: unknown

Published: Nov. 2, 2023

The transition metal-catalyzed enantioselective C-H functionalization strategy has revolutionized the logic of natural product synthesis. However, previous applications have heavily relied on use noble metal catalysts such as rhodium and palladium. Herein, we report efficient synthesis C1-chiral 1,2-dihydroisoquinolines (DHIQs) via C-H/N-H annulation picolinamides with alkynes catalyzed by a more sustainable cheaper 3d catalyst, cobalt(II) acetate tetrahydrate. A wide range enantiomerically enriched DHIQs were obtained in good yields excellent enantioselectivities (up to 98% yield >99% ee). robustness synthetic potential this method demonstrated modular asymmetric syntheses several tetrahydroisoquinoline alkaloids, including (S)-norlaudanosine, (S)-laudanosine, (S)-xylopinine, (S)-sebiferine, (S)-cryptostyline II, key intermediates (+)-solifenacin, FR115427, (+)-NPS R-568.

Language: Английский

Enantioselective C−H functionalization reactions enabled by cobalt catalysis DOI Creative Commons
Yang Zheng, Chao Zheng, Qing Gu

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(11), P. 2965 - 2985

Published: Sept. 16, 2022

Language: Английский

Citations

44
Ru(II)/Chiral Carboxylic Acid-Catalyzed Asymmetric [4 + 3] Annulation of Sulfoximines with α,β-Unsaturated Ketones DOI
Pu‐Fan Qian, Tao Zhou, Jun-Yi Li

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(22), P. 13876 - 13883

Published: Oct. 27, 2022

Sulfur-stereogenic containing benzo-fused heterocycles have gained much attention in drug discovery. However, the asymmetric synthesis of these chiral molecules with structural diversity is very challenging. Herein, we report benzothiadiazine-1-oxides a seven-membered ring via achiral Ru(II)-catalyzed [4 + 3] annulation sulfoximines α,β-unsaturated ketones assisted by carboxylic acid (CCA). A broad range benzothiadiazepine-1-oxides bearing various functional groups could be prepared up to 90% yield >99% ee, expanding chemical space sulfoximines. Notably, oxidative cleavage double bonds products gave N-benzoyl C–S axis.

Language: Английский

Citations

40
Cobalt-catalyzed enantioselective C–H/N–H annulation of aryl sulfonamides with allenes or alkynes: facile access to C–N axially chiral sultams DOI Creative Commons

Xiao‐Ju Si,

Xiaofang Zhao, Jianli Wang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(26), P. 7291 - 7303

Published: Jan. 1, 2023

Herein we report a cobalt-catalyzed enantioselective C-H/N-H annulation of aryl sulfonamides with allenes and alkynes, using either chemical or electrochemical oxidation. By O2 as the oxidant, proceeds efficiently low catalyst/ligand loading 5 mol% tolerates wide range allenes, including 2,3-butadienoate, allenylphosphonate, phenylallene, resulting in C-N axially chiral sultams high enantio-, regio-, position selectivities. The alkynes also exhibits excellent enantiocontrol (up to >99% ee) variety functional sulfonamides, internal terminal alkynes. Furthermore, oxidative is achieved simple undivided cell, demonstrating versatility robustness cobalt/Salox system. gram-scale synthesis asymmetric catalysis further highlight practical utility this method.

Language: Английский

Citations

36
Cobalt(III)-catalyzed asymmetric ring-opening of 7-oxabenzonorbornadienes via indole C–H functionalization DOI Creative Commons
Yang Zheng, Wenyun Zhang, Qing Gu

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Feb. 25, 2023

Abstract Asymmetric ring-opening of 7-oxabenzonorbornadienes is achieved via Co-catalyzed indole C–H functionalization. The utilization chiral Co-catalyst consisting a binaphthyl-derived trisubstituted cyclopentadienyl ligand resulted in high yields (up to 99%) and excellent enantioselectivity (>99% ee) for the target products with tolerance diverse functional groups. Opposite diastereoselectivities are obtained or Cp*CoI 2 CO. Combined experimental computational studies suggest β -oxygen elimination being selectivity-determining step reaction. Meanwhile, reactions 7-azabenzonorbornadiene could also be executed diastereodivergent manner.

Language: Английский

Citations

31
Data-driven design of new chiral carboxylic acid for construction of indoles with C-central and C–N axial chirality via cobalt catalysis DOI Creative Commons
Zijing Zhang, Shuwen Li, João C. A. Oliveira

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 31, 2023

Challenging enantio- and diastereoselective cobalt-catalyzed C-H alkylation has been realized by an innovative data-driven knowledge transfer strategy. Harnessing the statistics of a related transformation as source, designed machine learning (ML) model took advantage delta enabled accurate extrapolative enantioselectivity predictions. Powered model, virtual screening broad scope 360 chiral carboxylic acids led to discovery new catalyst featuring intriguing furyl moiety. Further experiments verified that predicted acid can achieve excellent stereochemical control for target alkylation, which supported expedient synthesis large library substituted indoles with C-central C-N axial chirality. The reported approach provides powerful data engine accelerate molecular catalysis harnessing hidden value available structure-performance statistics.

Language: Английский

Citations

31
Synthesis of Axially Chiral Biaryls through Cobalt(II)‐Catalyzed Atroposelective C−H Arylation DOI

Yong‐Jie Wu,

Zhen‐Kai Wang,

Zhen‐Sheng Jia

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 16, 2023

Highly efficient synthesis of axially chiral biaryl amines through cobalt-catalyzed atroposelective C-H arylation using easily accessible cobalt(II) salt and salicyloxazoline ligand has been reported. This methodology provides a straightforward sustainable access to broad range enantioenriched biaryl-2-amines in good yields (up 99 %) with excellent enantioselectivities % ee). The synthetic utility the unprecedented method is highlighted by its scalability diverse transformations.

Language: Английский

Citations

31
Copper-catalyzed asymmetric C(sp2)–H arylation for the synthesis of P- and axially chiral phosphorus compounds DOI Creative Commons

Shaobai Yan,

Rui Wang,

Zha-Gen Li

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 20, 2023

Transition metal-catalyzed C-H bond functionalization is an important method in organic synthesis, but the development of methods that are lower cost and have a less environmental impact desirable. Here, Cu-catalyzed asymmetric C(sp

Language: Английский

Citations

26
Enantioselective C–H bond functionalization under Co(iii)-catalysis DOI

Bholanath Garai,

Abir Das,

Doppalapudi Vineet Kumar

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(25), P. 3354 - 3369

Published: Jan. 1, 2024

Enantioselective C–H functionalization relies on 4d and 5d metals, but with their depletion, sustainable alternatives using 3d metals are crucial.

Language: Английский

Citations

13
Cobalt-Catalyzed Domino Transformations via Enantioselective C–H Activation/Nucleophilic [3 + 2] Annulation toward Chiral Bridged Bicycles DOI

Fan‐Rui Huang,

Qi‐Jun Yao, Peng Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15576 - 15586

Published: May 16, 2024

Selective synthesis of chiral bridged (hetero)bicyclic scaffolds via asymmetric C–H activation constitutes substantial challenges due to the multiple reactivities strained bicyclic structures. Herein, we develop domino transformations through an unprecedented cobalt-catalyzed enantioselective activation/nucleophilic [3 + 2] annulation with symmetrical alkenes. The methods offer straightforward access a wide range molecules bearing [2.2.1]-bridged cores four and five consecutive stereocenters in single step. Two elaborate salicyloxazoline (Salox) ligands were synthesized based on rational design mechanistic understanding. well-defined pockets generated from coordination around trivalent cobalt catalyst direct orientation alkenes, leading excellent enantioselectivity.

Language: Английский

Citations

9
Noncovalent interaction with a spirobipyridine ligand enables efficient iridium-catalyzed C–H activation DOI Creative Commons
Yushu Jin,

Ramadoss Boobalan,

Sobi Asako

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 17, 2024

Abstract Exploitation of noncovalent interactions for recognition an organic substrate has received much attention the design metal catalysts in synthesis. The CH–π interaction is especially interest molecular because both C–H bonds and π electrons are fundamental properties molecules. However, their weak nature, these have been less utilized control reactions. We show here that can be used to kinetically accelerate catalytic activation arenes by directly recognizing π-electrons arene substrates with a spirobipyridine ligand. Computation ligand kinetic isotope effect study provide evidence between backbone substrate. rational exploitation will open new avenues catalysis.

Language: Английский

Citations

8