Base-Promoted Ring-Opening Hydroxylation of Cyclic Sulfonium Salts DOI
Ziyu Wang,

Zeyu Shao,

Cheng Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3084 - 3091

Published: Feb. 9, 2024

Herein, we reported a general strategy for the synthesis of sulfur-containing primary alcohol derivatives by base-promoted ring-opening hydroxylation cyclic sulfonium salts. A variety salts were successfully transformed into desired hydroxylated products in moderate to excellent yields with good functional group tolerance. Moreover, one-pot synthesis, scale-up reaction, and late-stage functionalization complex molecules demonstrated practicability this synthetic protocol field chemistry.

Language: Английский

Using nature’s blueprint to expand catalysis with Earth-abundant metals DOI
R. Morris Bullock, Jingguang G. Chen, Laura Gagliardi

et al.

Science, Journal Year: 2020, Volume and Issue: 369(6505)

Published: Aug. 14, 2020

Making chemistry less precious Much of modern relies on catalysis by metals such as platinum, palladium, and rhodium. By contrast, more abundant iron copper suffice in biochemistry. Bullock et al. review the opportunities presented from study enzymes to shift balance synthetic catalysts further toward use these metals. Whether modifying themselves or designing ligand support architectures that take advantage cheaper metals' characteristic electron transfer properties, recent work points substantial progress. Science , this issue p. eabc3183

Language: Английский

Citations

447
Enantioselective Radical Reactions Using Chiral Catalysts DOI
Shovan Mondal, Frédéric Dumur, Didier Gigmès

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 5842 - 5976

Published: Jan. 24, 2022

Benefiting from the impressive increase in fundamental knowledge, last 20 years have shown a continuous burst of new ideas and consequently plethora catalytic methods for enantioselective radical reactions. This review aims to provide complete survey progress achieved over this latter period. The first part focuses on use chiral organocatalysts, these include catalysts covalently linked substrate those that interact with by weaker interactions like hydrogen bonds. second is devoted transition-metal redox catalysis which organized according increasing atomic number first-row transition metals (Ti, Cr, Fe, Mn, Co, Ni, Cu). Bioinspired manganese- iron-mediated hydroxylations oxidations are also discussed. A specific section dedicated reactivity Ru, Rh, Ir complexes as Lewis acids special focus at metal. Absorption photons result different events such energy transfer, single-electron hydrogen-atom transfer facilitating formation radicals. Organocatalysis has been successfully combined photocatalysts, opened pathways enlarging precursors available. merger photocatalysis organo- or metalla-photocatalysis brought novelty allowed discovery large original transformations. enzyme-catalyzed reactions involving intermediates largely benefit visible-light irradiation included review. provides comprehensive inventory goal detailing reaction mechanisms involved transformations any nonspecialist could find their own creativity invent yet unknown applications.

Language: Английский

Citations

253
Titanium catalysis for the synthesis of fine chemicals – development and trends DOI
Manfred Manßen, Laurel L. Schafer

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(19), P. 6947 - 6994

Published: Jan. 1, 2020

Atlas as a Titan(ium) is holding the earth-abundant chemistry world. Titanium second most abundant transition metal, key player in important industrial processes (e.g. polyethylene) and shows much promise for diverse applications future.

Language: Английский

Citations

143
Metalloradical approach for concurrent control in intermolecular radical allylic C−H amination DOI
Pan Xu, Jingjing Xie, Duo‐Sheng Wang

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(4), P. 498 - 507

Published: Jan. 12, 2023

Language: Английский

Citations

64
Iron(III)-based metalloradical catalysis for asymmetric cyclopropanation via a stepwise radical mechanism DOI
Wan‐Chen Cindy Lee, Duo‐Sheng Wang, Yiling Zhu

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(11), P. 1569 - 1580

Published: Sept. 7, 2023

Language: Английский

Citations

57
Metalloradical Catalysis: General Approach for Controlling Reactivity and Selectivity of Homolytic Radical Reactions DOI Creative Commons
Wan‐Chen Cindy Lee, X. Peter Zhang

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

Published: March 13, 2024

Abstract Since Friedrich Wöhler's groundbreaking synthesis of urea in 1828, organic over the past two centuries has predominantly relied on exploration and utilization chemical reactions rooted two‐electron heterolytic ionic chemistry. While one‐electron homolytic radical chemistry is both rich fundamental reactivities attractive with practical advantages, synthetic application been long hampered by formidable challenges associated control reactivity selectivity high‐energy intermediates. To fully harness untapped potential for synthesis, there a pressing need to formulate radically different concepts broadly applicable strategies address these outstanding issues. In pursuit this objective, researchers have actively developing metalloradical catalysis (MRC) as comprehensive framework guide design general approaches controlling stereoselectivity reactions. Essentially, MRC exploits metal‐centered radicals present open‐shell metal complexes catalysts activation substrates generate metal‐entangled key intermediates govern reaction pathway stereochemical course subsequent catalytic processes. Different from conventional transition complexes, operates through utilizing stepwise mechanisms.

Language: Английский

Citations

28
Catalyzing the Hydrodefluorination of CF3-Substituted Alkenes by PhSiH3. H• Transfer from a Nickel Hydride DOI
Chengbo Yao, Shuai Wang, Jack R. Norton

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(10), P. 4793 - 4799

Published: Jan. 14, 2020

The hydrodefluorination of CF3-substituted alkenes can be catalyzed by a nickel(II) hydride bearing pincer ligand. catalyst loading as low 1 mol%. gem-Difluoroalkenes containing number functional groups formed in good to excellent yields radical mechanism initiated H• transfer from the nickel hydride. relative reactivity various substrates supports proposed mechanism, does TEMPO trapping experiment.

Language: Английский

Citations

127
Recent Advances in Titanium Radical Redox Catalysis DOI
Terry McCallum, Xiangyu Wu, Song Lin

et al.

The Journal of Organic Chemistry, Journal Year: 2019, Volume and Issue: 84(22), P. 14369 - 14380

Published: Oct. 24, 2019

New catalytic strategies that leverage single-electron redox events have provided chemists with useful tools for solving synthetic problems. In this context, Ti offers opportunities are complementary to late transition metals reaction discovery. Following foundational work on epoxide reductive functionalization, recent methodological advances significantly expanded the repertoire of radical chemistry. This Synopsis summarizes developments in burgeoning area catalysis a focus innovative such as redox-relay and dual catalysis.

Language: Английский

Citations

116
Enantioselective Radical Construction of 5-Membered Cyclic Sulfonamides by Metalloradical C–H Amination DOI
Yang Hu, Kai Lang, Chaoqun Li

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(45), P. 18160 - 18169

Published: Oct. 17, 2019

Both arylsulfonyl and alkylsulfonyl azides can be effectively activated by the cobalt(II) complexes of D2-symmetric chiral amidoporphyrins for enantioselective radical 1,5-C–H amination to stereoselectively construct 5-membered cyclic sulfonamides. In addition C–H bonds with varied electronic properties, Co(II)-based metalloradical system features chemoselective allylic is compatible heteroaryl groups, producing functionalized sulfonamides in high yields enantioselectivities. The unique profile reactivity selectivity Co(II)-catalyzed attributed its underlying stepwise mechanism, which supported several lines experimental evidence.

Language: Английский

Citations

108
Enantioselective Intermolecular Radical C–H Amination DOI
Li‐Mei Jin, Pan Xu, Jingjing Xie

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(49), P. 20828 - 20836

Published: Nov. 25, 2020

Radical reactions hold a number of inherent advantages in organic synthesis that may potentially impact the planning and practice for construction molecules. However, control enantioselectivity radical processes remains one longstanding challenges. While significant advances have recently been achieved intramolecular reactions, governing asymmetric induction intermolecular still poses challenging issues. We herein report catalytic approach is highly effective controlling as well reactivity C–H amination carboxylic acid esters with azides via Co(II)-based metalloradical catalysis (MRC). The key to success lies catalyst development maximize noncovalent attractive interactions through fine-tuning remote substituents D2-symmetric chiral amidoporphyrin ligand. This interaction strategy presents solution be generally applicable reactions. Co(II)-catalyzed amination, which operates under mild conditions substrate limiting reagent, exhibits broad scope high chemoselectivity, providing access valuable amino derivatives enantioselectivities. Systematic mechanistic studies shed light into working details underlying stepwise pathway amination.

Language: Английский

Citations

97