Organic Letters, Год журнала: 2024, Номер unknown
Опубликована: Дек. 23, 2024
A copper-catalyzed [2,3]-sigmatropic rearrangement of azide-ynamides via selenium ylides is disclosed, which leads to the practical and divergent synthesis a variety tricyclic heterocycles bearing quaternary carbon stereocenter in generally moderate excellent yields. Significantly, this method represents first ylide based on alkynes an unprecedented α-imino copper carbenes.
Язык: Английский
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)
Опубликована: Март 30, 2023
Axially chiral biaryls widely exist in natural products and pharmaceuticals are used as ligands catalysts asymmetric synthesis. Compared to the well-established axially 6-membered biaryl skeletons, examples of 5-membered have been quite scarce, mono-substituted 3-arylpyrrole atropisomers not reported. Here, we disclose a copper-catalyzed atroposelective diyne cyclization for construction range arylpyrrole good excellent yields with generally enantioselectivities via oxidation X-H insertion vinyl cations. Importantly, this protocol only represents first synthesis atropisomers, but also constitutes example atropisomer Theoretical calculations further support mechanism cation-involved elucidate origin enantioselectivity.
Язык: Английский
Процитировано
32
Chemical Science, Год журнала: 2023, Номер 14(22), С. 5918 - 5924
Опубликована: Янв. 1, 2023
Catalytic enantioselective transformation of alkynes has become a powerful tool for the synthesis axially chiral molecules. Most these atroposelective reactions rely on transition-metal catalysis, and organocatalytic approaches are largely limited to special which act as precursors Michael acceptors. Herein, we disclose an intramolecular (4 + 2) annulation enals with ynamides. This method allows efficient highly atom-economical preparation various 7-aryl indolines in generally moderate good yields excellent enantioselectivities. Computational studies were carried out elucidate origins regioselectivity enantioselectivity. Furthermore, phosphine ligand derived from synthesized indoline was proven be potentially applicable asymmetric catalysis.
Язык: Английский
Процитировано
12
Green Chemistry, Год журнала: 2023, Номер 25(22), С. 9092 - 9096
Опубликована: Янв. 1, 2023
An efficient iron-catalyzed sulfur alkylation of sulfenamides with diazo compounds for the synthesis functionalized sulfilimines is developed under air conditions.
Язык: Английский
Процитировано
12
Science China Chemistry, Год журнала: 2024, Номер 67(9), С. 2982 - 2988
Опубликована: Июль 3, 2024
Язык: Английский
Процитировано
4
Chemical Society Reviews, Год журнала: 2025, Номер unknown
Опубликована: Янв. 1, 2025
This review summarizes the latest trends and developments of isoxazole-enabled alkyne amination reactions their applications in divergent heterocycle synthesis.
Язык: Английский
Процитировано
0
Organic Letters, Год журнала: 2025, Номер unknown
Опубликована: Март 26, 2025
The [2,3]-sigmatropic rearrangement has been widely utilized to construct C-S bonds. Herein, we report an enantioselective, intermolecular, and noncarbenoid of sulfonium ylides using azoalkenes. This process features a broad substrate scope, high efficiency, excellent enantioselectivity, achieving yields up 99% enantiomeric excess (ee) 96%. Furthermore, the protocol demonstrated good scalability.
Язык: Английский
Процитировано
0
Organic Letters, Год журнала: 2023, Номер 25(12), С. 2063 - 2067
Опубликована: Март 20, 2023
A novel copper-catalyzed tandem cyclization/direct C(sp2)–H annulation of phenyl azide–ynamides via α-imino copper carbenes has been developed, which provides a concise and flexible approach for the construction range valuable azepino[2,3-b:4,5-b′]diindoles in mostly good to excellent yields with high chemoselectivities. This reaction also exhibits broad substrate scope, functional group tolerance, simple operation, mild conditions.
Язык: Английский
Процитировано
9
ACS Catalysis, Год журнала: 2023, Номер 13(13), С. 8803 - 8812
Опубликована: Июнь 19, 2023
Herein, an organocatalytic enantioselective desymmetrizing hydroalkoxylation of 1,4- and 1,8-diynes is disclosed, which represents a unique chiral Brønsted acid-catalyzed desymmetrization diynes. This protocol provides facile practical access to enantioenriched 1,3-diaminopropanol derivatives γ-butyrolactones with wide substrate scope generally high enantioselectivities. Besides, the backbones these products constitute structural core numerous bioactive molecules, they can serve as valuable precursors for expeditious assembly versatile N- O-heterocycles. Moreover, control experiments theoretical calculations are employed confirm mechanistic rationale elucidate origin enantioinduction.
Язык: Английский
Процитировано
8
Chemistry - A European Journal, Год журнала: 2023, Номер 29(70)
Опубликована: Сен. 28, 2023
Abstract Gold catalysis is an important method for alkyne functionalization. Here we report the gold‐catalyzed formal [3+2] aminative cyclization of yndiamides and isoxazoles in a direct synthesis polysubstituted diaminopyrroles, which are motifs drug discovery. Key to this process formation, subsequent cyclization, α‐imino gold Fischer carbene, represents new type carbene intermediate. The reaction proceeds rapidly under mild conditions, with high regioselectivity being achieved by introducing subtle steric bias between nitrogen substituents on yndiamide. DFT calculations revealed that key was interconversion isomeric keteniminiun ions via low‐barrier π‐complex transition state, establishes Curtin‐Hammett scenario isoxazole addition. By using benzisoxazoles as substrates, outcome could be switched [5+2] leading 1,4‐oxazepines.
Язык: Английский
Процитировано
8
Science Advances, Год журнала: 2023, Номер 9(51)
Опубликована: Дек. 20, 2023
Here, an Ir/Zn-cocatalyzed atroposelective [2+2+2] cycloaddition of 1,6-diynes and ynamines was developed, forging various functionalized C─N axially chiral indoles pyrroles in generally good to excellent yields (up 99%), chemoselectivities, high enantioselectivities 98% enantiomeric excess) with wide substrate scope. This cocatalyzed strategy not only provided alternative promising reliable way for asymmetric alkyne cyclotrimerization easy handle but also settled the issues previous [Rh(COD)2]BF4-catalyzed system on construction axial chirality such as complex operations, limited scope, low efficiency. In addition, control experiments theoretical calculations disclosed that Zn(OTf)2 markedly reduced barrier migration insertion significantly increase reaction efficiency, which distinctly different from work Lewis acid improving yield through accelerating oxidative addition reductive elimination.
Язык: Английский
Процитировано
8