Acylsilane Directed Rh-Catalyzed Arene C–H Alkylation with Maleimides and Visible-Light-Induced Siloxycarbene-Amide Cyclization: [3 + 2] Carbo-Annulation in Ru Catalysis

Organic Letters, Год журнала: 2023, Номер 25(15), С. 2594 - 2599

Опубликована: Апрель 10, 2023

We herein demonstrate the acylsilane-directed Rh-catalyzed arene C–H bond alkylation with maleimides. The resulting derivatives were utilized in visible-light-induced intramolecular siloxycarbene-amide cyclization for synthesis of new tricyclic γ-lactams. In parallel, we also harnessed same acylsilane and maleimide units through [3 + 2] carbo-annulation by using Ru-catalysis. A wide range maleimides aroylsilanes used to establish broadness these transformations.

Язык: Английский

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Visible-light-promoted defluorinated alkylation of trifluoromethyl alkenes initiated by radical [1,2]-Brook rearrangement: facile synthesis ofgem-difluoro homoallylic alcohol derivatives

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(8), С. 1981 - 1987

Опубликована: Янв. 1, 2023

A photoinduced radical [1,2]-Brook rearrangement/defluorinated alkylation reaction of α-trifluoromethyl alkenes with α-silyl alcohols was developed for facile access to gem -difluoro homoallylic alcohol derivatives.

Язык: Английский

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Carbene Formation or Reduction of the Diazo Functional Group? An Unexpected Solvent‐Dependent Reactivity of Cyclic Diazo Imides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Июль 28, 2023

The control of the reactivity diazo compounds is commonly achieved by choice a suitable catalyst, e.g. via stabilization singlet carbenes or radical intermediates. Herein, we report on light-promoted cyclic imides with thiols, where solvent results in two fundamentally different reaction pathways. In dichloromethane (DCM), carbene formed initially and engages cascade C-H functionalization/thiolation to deliver indane-fused pyrrolidines good excellent yields. When switching acetonitrile solvent, pathway shut down an unusual reduction compound occurs under otherwise identical conditions, aryl thiol acts as reductant. A combined set experimental computational studies was carried out obtain mechanistic understanding support that indane formation proceeds insertion triplet carbene, while electron transfer process.

Язык: Английский

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Synthesis of Organofluorine Compounds with Acylsilanes^†

Chinese Journal of Chemistry, Год журнала: 2023, Номер 42(8), С. 887 - 902

Опубликована: Ноя. 29, 2023

Comprehensive Summary Organofluorine compounds are central in synthetic chemistry, medicinal chemistry and material chemistry. In this review, we summarize the investigations on synthesis of organofluorine with acylsilanes. For non‐fluorinated acylsilanes, situ generation difluoroenoxysilanes from reactions acylsilanes trifluoromethylation reagents is major pathway, leading to facile preparation various α,α‐difluoroketones. fluoroalkylacylsilanes, apart through anion Brook rearrangement, radical rearrangement photoexcited selective control reactivities biradicals pave way for a variety compounds. general, most these gave racemic products, asymmetric still rare, which would be future direction field. Key Scientists 1957, first acylsilane compound, triphenylsilyl phenyl ketone was reported by group. 1991, Portella coworkers reaction perfluoroorganometallic without resulting formation alcohols as products. 1992, Xu carried out investigation fluoroalkylacylsilanes rearrangement. 1994, group Ruppert‐Prakash reagent. 2009, Otaka NHC‐mediated intramolecular redox prepare ( Z )‐fluoroalkene dipeptide isosteres (FADIs) γ,γ‐difluoro‐α,β‐ enoylsilane. Until 2022, application fluoroalkylsiloxycarbenes achieved Shen group, enabling fluoroalkylated cyclopropenols. successfully trapping biradical intermediates generated fluorine‐containing fused gem ‐difluorooxetanes. same year, asymetric enantiomerically enriched fluoroalkyl difluoroenoxysilanes.

Язык: Английский

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Difluoromethyl phenoxathiinium salt: A new general and versatile difluoromethylating reagent with divergent ·CF2H, CF2H+, and:CF2 reactivities

Science China Chemistry, Год журнала: 2023, Номер 67(3), С. 953 - 962

Опубликована: Дек. 27, 2023

Язык: Английский

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