Nickel-Catalyzed Hydrofluorination in Unactivated Alkenes: Regio- and Enantioselective C–F Bond Formation DOI
Changseok Lee, Minseok Kim, Seunghoon Han

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9375 - 9384

Published: March 21, 2024

Catalytic formation of a regio- and enantioselective C–F bond chiral center from readily available alkenes is crucial goal, yet it continues to pose significant challenges in organic synthesis. Here, we report the regioselective bonds facilitated by NiH catalysis coordination directing strategy that enables precise hydrofluorination both terminal internal alkenes. Notably, have optimized this methodology achieve high enantioselectivity creating aliphatic stereogenic centers especially with β,γ-alkenyl substrates, using tailored Bn-BOx ligand. Another pivotal finding our research identification (+)-nonlinear effect under conditions, allowing for even moderately enantiomerically enriched ligands. Given role fluorine pharmaceuticals synthetic materials, offers essential insights into centers, paving way efficient production valuable fluorinated compounds.

Language: Английский

Asymmetric alkyl-alkyl cross-coupling enabled by earth-abundant metal-catalyzed hydroalkylations of olefins DOI Creative Commons
Pengfei Yang, Wei Shu

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(4), P. 100508 - 100508

Published: Jan. 30, 2023

Language: Английский

Citations

28
Cobalt(II)‐Catalyzed C(sp3)−C(sp3) Coupling for the Direct Stereoselective Synthesis of 2‐Deoxy‐C‐Glycosides from Glycals DOI
Mingjie Zeng, Changyue Yu, Yibing Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(22)

Published: March 17, 2023

We report a ligand-controlled CoII -catalyzed C(sp3 )-C(sp3 ) coupling hydroalkylation for direct and β-selective synthesis of 2-deoxy-C-glycosides from glycals. This reaction proceeds by radical pathway alkyl halide activation is through ligand control. approach may inspire the development further stereoselective reactions with potential application in field carbohydrates.

Language: Английский

Citations

28
Cobalt‐Catalyzed Facial‐Selective Hydroalkylation of Cyclopropenes DOI
Zhilin Zhang, Zhen Li,

Yuantai Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: May 31, 2023

Abstract Cyclopropene hydrofunctionalization has been a promising strategy for accessing multi‐substituted cyclopropanes; however, cyclopropene hydroalkylation remains underdeveloped. Herein, we report low‐valent CoH‐catalyzed facial‐selective to access cyclopropanes. This reaction exhibits broad substrate scope of alkyl halides and cyclopropenes tolerates many functional groups. Moderate‐to‐good facial‐selectivity is obtained without any directing Mechanism studies provide evidence that radicals are generated from irreversible CoH insertion responsible the facial‐selectivity. Our preliminary exploration demonstrates asymmetric can be realized conspicuous auxiliary

Language: Английский

Citations

26
Enantioselective Directed Nickel-Catalyzed Three-Component Reductive Arylalkylation of Alkenes via the Carbometalation/Radical Cross-Coupling Sequence DOI

Zhan Dong,

Changyu Xu,

Jianchao Chang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4395 - 4406

Published: March 8, 2024

Asymmetric reductive three-component arylalkylation of alkenes via the radical relay method has been well established, while asymmetric migratory insertion strategy remains unexplored. We report enantioselective nickel-catalyzed cross-electrophile with aryl- and alkyl halides an integrated Heck carbometalation/radical cross-coupling sequence. This protocol employing a chiral Ni/PHOX catalytic system allows terminal internal to successfully engage exquisite control regio-, chemo-, stereoselectivity. More importantly, this undergoes regio- arylnickelation followed by Csp3–Csp3 elimination, thus exhibiting reverse regioselectivity method. Mild reaction conditions exceptional functional group tolerance facilitate method's compatibility bioactive motifs modular synthesis biologically active compounds. The experiments density theory calculations provide insights into mechanism origin stereoselectivity, hemilabile nature PHOX ligand is critical for achieving arylalkylation.

Language: Английский

Citations

11
Nickel-Catalyzed Hydrofluorination in Unactivated Alkenes: Regio- and Enantioselective C–F Bond Formation DOI
Changseok Lee, Minseok Kim, Seunghoon Han

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9375 - 9384

Published: March 21, 2024

Catalytic formation of a regio- and enantioselective C–F bond chiral center from readily available alkenes is crucial goal, yet it continues to pose significant challenges in organic synthesis. Here, we report the regioselective bonds facilitated by NiH catalysis coordination directing strategy that enables precise hydrofluorination both terminal internal alkenes. Notably, have optimized this methodology achieve high enantioselectivity creating aliphatic stereogenic centers especially with β,γ-alkenyl substrates, using tailored Bn-BOx ligand. Another pivotal finding our research identification (+)-nonlinear effect under conditions, allowing for even moderately enantiomerically enriched ligands. Given role fluorine pharmaceuticals synthetic materials, offers essential insights into centers, paving way efficient production valuable fluorinated compounds.

Language: Английский

Citations

11