Organic Letters, Journal Year: 2024, Volume and Issue: 26(36), P. 7661 - 7666
Published: Aug. 28, 2024
A photoreductive halogen-atom transfer (XAT) strategy for 1,4-dicarbofunctionalization of 1,3-enynes with organoiodides and cyanoarenes is disclosed, enabling access to functionalized allenes in a highly regio-, chemo-, stereoselective manner. Upon the photoredox catalysis activation Et
Language: Английский
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)
Published: June 18, 2024
Described herein is a dirhodium(II)-catalyzed silylation of propargyl esters with hydrosilanes, using tertiary amines as axial ligands. By adopting this strategy, range versatile and useful allenylsilanes can be achieved good yields. This reaction not only represents S
Language: Английский
Citations
7
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(20), P. 15790 - 15798
Published: Oct. 10, 2024
Here, we report a photoredox and nickel-catalyzed cross-electrophile coupling strategy for the asymmetric three-component 1,2-alkylarylation of vinyl boronates with (hetero)aryl bromides (2°, 3°)-alkyl redox-active esters in presence Hantzsch ester. With fluorinated pyridyl-substituted chiral biimidazoline ligand, this reaction enables straightforward access to wide variety synthetically valuable α-aryl from readily available starting materials. This features mild conditions, broad substrate generality, good functional group tolerance proceeds without using metal reductants or alkyl halides. Furthermore, alkenyl halides other electron-deficient alkenes such as acrylates phosphonates can be applied successfully. Preliminary mechanistic studies shed light on potential pathways roles organic amines.
Language: Английский
Citations
7
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)
Published: Nov. 13, 2023
Abstract The development of metal complexes that function as both photocatalyst and cross‐coupling catalyst remains a challenging research topic. So far, progress has been shown in palladium(0) excited‐state transition catalysis for the construction carbon‐carbon bonds where oxidative addition alkyl/aryl halides to zero‐valent palladium (Pd 0 ) is achievable at room temperature. In contrast, analogous process with divalent II uphill endothermic. For first time, we report can act light‐absorbing species undergoes double excitation realize carbon‐nitrogen (C−N) cross‐couplings under air. Differently substituted aryl be applied mild, selective amination using acetate Density functional theory studies supported by mechanistic investigations provide insight into reaction mechanism.
Language: Английский
Citations
16
The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 2885 - 2894
Published: Feb. 14, 2024
Because of their various reactivities, propargyl acetates are refined chemical intermediates that extensively applied in pharmaceutical synthesis. Currently, reactions between and chlorosilanes may be the most effective method for synthesizing silylallenes. Nevertheless, owing to adaptability selectivity substrates, transition metal catalysis is difficult achieve. Herein, nickel-catalyzed reductive cross-coupling substituted vinyl synthesis tetrasubstituted silylallenes described. Therein, metallic zinc a crucial reductant effectively enables two electrophilic reagents selectively construct C(sp2)–Si bonds. Additionally, Ni-catalyzed mechanism involving radical process proposed on basis deuteration-labeled experiments.
Language: Английский
Citations
6
Organic Letters, Journal Year: 2023, Volume and Issue: 25(39), P. 7263 - 7267
Published: Sept. 27, 2023
An electroreductive cross-coupling of prop-2-yn-1-yl acetates with chloro(vinyl)silanes for producing tetrasubstituted silylallenes is developed. The method enables the formation a new C─Si bond through cathodic reduction silyl radical, radical addition across C≡C bond, alkenyl anion intermediate formation, and deacetoxylation represents mild, practical route to synthesis silylallenes. Mechanistic studies reveal that CoCl2 acts as mediator promote via electron transfer.
Language: Английский
Citations
12
Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(12), P. 100819 - 100819
Published: Nov. 22, 2023
Language: Английский
Citations
12
Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(17), P. 2023 - 2028
Published: April 30, 2024
Comprehensive Summary A general and broadly applicable copper photoredox dual‐catalyzed multicomponent 1,4‐perfluoroalkylcyanation of 1,3‐enynes has been developed. This protocol enjoys success with high regioselectivity, mild reaction conditions, excellent functional‐group tolerance, allowing the facile synthesis structurally diverse perfluoroalkylated allenes from readily available fluoroalkyl halides, TMSCN in a one‐pot manner. reasonable mechanism proposed according to series control experiments.
Language: Английский
Citations
5
Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3485 - 3490
Published: Jan. 1, 2024
Herein, we report electrochemically mediated trifluoromethylallene synthesis via the rearrangement of trifluoromethyl-containing 1,3-enynes under action silicon or boron radicals, with good selectivity and without external oxidants.
Language: Английский
Citations
5
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)
Published: July 3, 2024
Skeletal molecular editing gained considerable recent momentum and emerged as a uniquely powerful tool for late-stage diversifications. Thus far, superstoichiometric amounts of costly hypervalent iodine(III) reagents were largely required skeletal indole editing. In contrast, we herein show that electricity enables sustainable nitrogen atom insertion reactions to give bio-relevant quinazoline scaffolds without stoichiometric chemical redox-waste product. The transition metal-free electro-editing was enabled by the oxygen reduction reaction (ORR) proved robust on scale, while tolerating variety valuable functional groups.
Language: Английский
Citations
5
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(51)
Published: Aug. 28, 2024
Abstract Bicyclo[1.1.1]pentane (BCP), recognized as a bioisostere for para ‐disubstituted benzene, has gained widespread interest in drug development due to its ability enhance the physicochemical properties of pharmaceuticals. In this work, we introduce photoinduced, halogen bonding‐initiated, metal‐free strategy synthesizing various BCP derivatives. This method involves generation nucleophilic α‐aminoalkyl radicals via halogen‐bonding adducts. These undergo selective radical addition [1.1.1]propellane, yielding electrophilic that subsequently participate polarity‐matched additions, culminating difunctionalization bicyclopentane. The versatility and practicality approach are underscored by broad substrate scope, which includes late‐stage functionalization series valuable transformations, all conducted under mild reaction conditions.
Language: Английский
Citations
5