Elsevier eBooks, Journal Year: 2023, Volume and Issue: unknown
Published: Jan. 1, 2023
Language: Английский
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: March 7, 2025
The formation of sterically hindered C(sp2)-C(sp3) bonds could be a useful synthetic tool but has been understudied in cross-electrophile coupling. Here, we report two methods that couple secondary alkyl bromides with aryl halides contain C-X bonds: 1) ortho-substituted nickel catalysts and 2) di-ortho-substituted iodides cobalt catalysts. Stoichiometric experiments deuterium labeling studies show [Co] is better than [Ni] for oxidative addition Ar-I radical capture/reductive elimination steps arenes. For both metals, Ar-H side products observed reactions low-yielding appear to arise from Ar• hydrogen-atom transfer the solvent. While origins differences scope are not yet understood, these demonstrate previously unknown complementarity between
Language: Английский
Citations
0
Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown
Published: March 8, 2025
Comprehensive Summary Herein, we present the first examples of asymmetric reductive 1,4‐dicarbofunctionalization 1,3‐dienes and 1,5‐dicarbofunctionalization vinylcyclopropanes, which proceed under catalysis a chiral nickel/bis‐imidazoline complex using alkyl halides aryl iodides or alkenyl bromides as electrophilic coupling partners. In these highly enantioselective transformations operating in radical relay mechanism, C(sp 3 )‐ 2 )‐type carbo‐moieties are respectively installed on terminal internal position with newly formed olefinic unit high E ‐selectivity.
Language: Английский
Citations
0
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown
Published: Sept. 16, 2024
Selective functionalization of ubiquitous C-H bonds based on 1,
Language: Английский
Citations
2
Organic Letters, Journal Year: 2024, Volume and Issue: unknown
Published: Sept. 27, 2024
Asymmetric aza-Heck cyclization and coupling reactions offer efficient access to enantioenriched
Language: Английский
Citations
2
Cell Reports Physical Science, Journal Year: 2024, Volume and Issue: unknown, P. 102248 - 102248
Published: Oct. 1, 2024
Language: Английский
Citations
2
Chem Catalysis, Journal Year: 2023, Volume and Issue: 4(1), P. 100798 - 100798
Published: Nov. 7, 2023
Language: Английский
Citations
4
Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(25)
Published: Jan. 22, 2024
Abstract β‐Tertiary amino acid derivatives constitute one of the most frequently occurring units in natural products and bioactive molecules. However, efficient asymmetric synthesis this motif still remains a significant challenge. Herein, we disclose cobalt‐catalyzed enantioselective reductive addition reaction ketimine using α‐chloro carbonyl compound as radical precursor, providing expedient access to diverse array enantioenriched β‐quaternary analogues. This protocol exhibits outstanding enantioselectivity broad substrate scope with excellent functional group tolerance. Preliminary mechanism studies rule out possibility Reformatsky‐type confirm involvement species stereoselective process. The synthetic utility has been demonstrated through rapid assembly iterative oligopeptide, showcasing its versatile platform for late‐stage modification drug candidates.
Language: Английский
Citations
1
Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(22), P. 6311 - 6318
Published: Jan. 1, 2024
Co-catalyzed asymmetric reductive addition of ketimine with cyclopropyl chloride has been realized to access diverse chiral amino esters bearing fragments broad functional group tolerance and excellent enantioselectivities.
Language: Английский
Citations
1
Science Advances, Journal Year: 2023, Volume and Issue: 9(51)
Published: Dec. 20, 2023
The development of a reliable method for asymmetric synthesis unnatural peptides is highly desirable and particularly challenging. In this study, we present versatile efficient approach that uses cobalt-catalyzed diastereoselective umpolung hydrogenation to access noncanonical aryl alanine peptides. This protocol demonstrates good tolerance toward various functional groups, amino acid sequences, peptide lengths. Moreover, the versatility reaction illustrated by its successful application in late-stage functionalization formal representative chiral natural products pharmaceutical scaffolds. strategy eliminates need synthesizing alanines before formation, does not result racemization or epimerization. underlying mechanism was extensively explored through deuterium labeling, control experiments, HRMS identification, UV-Vis spectroscopy, which supported reasonable CoI/CoIII catalytic cycle. Notably, acetic methanol serve as safe cost-effective hydrogen sources, while indium powder acts terminal electron source.
Language: Английский
Citations
2
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3241 - 3247
Published: Feb. 15, 2024
The unique low level of the ionization potential indium(0) to indium(I) makes it an appealing metal for organic synthesis. Here, we present indium-catalyzed reductive cross-coupling between chlorophosphines (R2PCl) or dichlorophosphines (RPCl2) with acyl chlorides (RCOCl). This one-pot approach, using indium-catalysis followed by oxidation, generates a variety mono- bis-acylphosphine oxides in good yields. Additionally, this protocol offers convenient pathway obtain photoinitiators, Luricin TPO and IRGACURE 819, that are widely used industry. Experimental computational studies indicate intermediacy phosphorus-based radical species dimerize diphosphines, which then couple through four-membered transition state. Furthermore, also explore homocoupling R2PCl RPCl2, provides facile access various P–P bond formations.
Language: Английский
Citations
0