Rhodium(II)-Catalyzed Asymmetric Cyclopropanation and Desymmetrization of [2.2]Paracyclophanes

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6423 - 6431

Опубликована: Апрель 11, 2024

Chiral [2.2]paracyclophane derivatives are of considerable interest because their potential in asymmetric catalysis and the development chiral materials. This study describes scope rhodium-catalyzed reactions aryldiazoacetates with [2.2]paracyclophanes. The reaction parent resulted cyclopropanation at two positions, ratio which is catalyst-controlled. Because strain system, one cyclopropanes exists primarily as norcaradiene structure, whereas other preferentially cycloheptatriene conformer. In contrast, [3.3]paracyclophane results benzylic C-H functionalization. substituted [2.2]paracyclophanes using catalysts can result either kinetic resolution or desymmetrization. Rh

Язык: Английский

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Visible-Light-Induced Dearomatization via [2+2] Cycloaddition or 1,5-Hydrogen Atom Transfer: Divergent Reaction Pathways of Transient Diradicals

ACS Catalysis, Год журнала: 2020, Номер 10(21), С. 12618 - 12626

Опубликована: Сен. 28, 2020

Visible-light-induced dearomatization reaction via energy-transfer mechanism is an emerging strategy for the synthesis of highly strained polycyclic molecules. Transient, high-energy diradical species are typically involved in this type as key intermediates. Herein, we report visible-light-induced divergent indole-tethered O-methyl oximes, which reactions open-shelled singlet intermediates toward competitive [2 + 2] cycloaddition or 1,5-hydrogen atom transfer can be achieved with exclusive selectivity. The has been well supported by a series experimental and computational investigations. allow facile structurally appealing indoline-fused azetidines related molecules high efficiency.

Язык: Английский

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Photochemical Doyle–Kirmse Reaction: A Route to Allenes

Organic Letters, Год журнала: 2020, Номер 22(3), С. 1018 - 1021

Опубликована: Янв. 3, 2020

This Letter describes the metal-free, blue-light-induced [2,3]-sigmatropic rearrangement of sulfonium ylides generated from donor/acceptor diazoalkanes and propargyl sulfides. The reaction furnishes highly functionalized allenes a broad range starting materials in decent yield. Mechanistic experiments supported by literature data suggest singlet carbenes as intermediates this reaction.

Язык: Английский

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Visible light and base promoted O-H insertion/cyclization of para-quinone methides with aryl diazoacetates: An approach to 2,3-dihydrobenzofuran derivatives

Chinese Chemical Letters, Год журнала: 2021, Номер 32(8), С. 2577 - 2581

Опубликована: Март 7, 2021

Язык: Английский

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Synthesis of trisubstituted hydroxylamines by a visible light-promoted multicomponent reaction

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(21), С. 5982 - 5987

Опубликована: Янв. 1, 2021

A green and efficient route for the synthesis of trisubstituted hydroxylamines from β-keto ester, 2-nitrosopyridine aryldiazoacetates has been reported. This multicomponent reaction occurred under mild conditions without catalysts or additives.

Язык: Английский

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