Rhodium(<scp>i</scp>)-catalyzed vinylation/[2 + 1] carbocyclization of 1,6-enynes with α-diazocarbonyl compounds

Huang, Jin‐Shun; Hu, Xinwei; Chen, Fengjuan; Gui, Jiao; Zeng, Wei

doi:10.1039/c9ob01028a

Cited by 5 publications

(3 citation statements)

References 55 publications

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“…In the same year, a [2+1] cycloaddition reaction of 1,6‐enynes with α ‐diazocarbonyl compounds as coupling partners for the assembly of various functionalized vinyl‐substituted azabicyclic[3.1.0]hexanes has been reported by the Zeng group (Scheme 82). [64] This reaction provided a atom economical method for the construction of fused polycycles employing [Rh(cod)Cl] 2 as the catalyst and dppp as the ligand. It is noteworthy that the transformation exhibited a wide functional group compatibility and greatly expanded the application of diazo compounds.…”

Section: Transition Metal Catalyzed Cyclization Of 16‐enynesmentioning

confidence: 99%

Recent Advances in Cyclization Reactions of 1,6‐Enynes

Liu,

Xu,

Han

et al. 2024

Adv Synth Catal

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Elaborated molecular architectures, specifically those bearing one or more carbon stereocenters, stand as an important class of carbocyclic and heterocyclic frameworks because they are frequently occurring core structures in numerous natural products and biologically active pharmaceutical molecules. Over the past few decades, the development of novel and versatile synthetic approaches via cascade cyclization reactions of 1,6‐enynes for the construction of a series of fused and spiro compounds has been the focus of a great deal of research initiatives. These synthesis strategies are peculiarly fascinating in the context of the assembly of a wide array of pharmaceutical molecules, natural products, agrochemicals, and functional materials. In this review, recent developments in the transformations of 1,6‐enynes with diverse coupling reagents are summarized since 2018, which could be divided into five categories: 1) Introduction; 2) Transition metal catalyzed cyclization of 1,6‐enynes; 3) Metal‐free cyclization of 1,6‐enynes; 4) Visible‐light‐induced cyclization of 1,6‐enynes; 5) Electrocatalytic cyclization of 1,6‐enynes.

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Section: Transition Metal Catalyzed Cyclization Of 16‐enynesmentioning

confidence: 99%

Recent Advances in Cyclization Reactions of 1,6‐Enynes

Liu,

Xu,

Han

et al. 2024

Adv Synth Catal

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“…[31] Several recent works reported the use of tandem metal-catalyzed cyclizations for the construction of the target bicyclic system (Scheme 1, D-F). [32,33,34] In this work, we report synthesis of a series of novel 6functionalized azabicyclo[4.1.0]heptane-derived medicinally relevant building blocks starting from a common readily available precursor -1-benzyl-4-hydroxymethyl-1,2,3,6-tetrahydropyridine (3) -that in turn can be prepared from commercially available 4-(hydroxymethyl)pyridine (1) (Scheme 2). [35] The construction of 3-azabicyclo[4.1.0]alkane ring system was envisaged through Simmons-Smith cyclopropanation of the non-activated double bound in key intermediate 3.…”

Section: Introductionmentioning

confidence: 99%

“…Later, an increased outcome of the target boronate was achieved through palladium‐catalyzed cyclopropanation of an unsaturated pinacol boronate with diazomethane (Scheme 1, C ) [31] . Several recent works reported the use of tandem metal‐catalyzed cyclizations for the construction of the target bicyclic system (Scheme 1, D – F ) [32,33,34] …”

Section: Introductionmentioning

confidence: 99%

Expedient Synthesis of 6‐Functionalized Azabicyclo[4.1.0]heptane Derivatives

Omelian,

Ostapchuk,

Dobrydnev

et al. 2023

ChemistrySelect

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An efficient approach to the synthesis of previously unreported azabicyclo[4.1.0]heptane‐derived building blocks is reported following the divergent strategy. The common synthetic precursor – tert‐butyl 6‐(hydroxymethyl)‐3‐azabicyclo[4.1.0]heptane‐3‐carboxylate was obtained in four steps with 38 % overall yield and was involved in short reaction sequences (1–3 steps) to provide the target bifunctional derivatives, including novel bicyclic N‐Boc protected γ‐amino acid. The described compounds are interesting in terms of lead‐likeness concepts, according to which the rigid 3D‐shaped and sp3‐enriched frameworks are among the most promising entry points for drug discovery projects.

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Controlling Enantioselectivity and Diastereoselectivity in Radical Cascade Cyclization for Construction of Bicyclic Structures

et al. 2021

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Radical cascade cyclization reactions are highly attractive synthetic tools for the construction of polycyclic molecules in organic synthesis. While it has been successfully implemented in diastereoselective synthesis of natural products and other complex compounds, radical cascade cyclization faces a major challenge of controlling enantioselectivity. As the first application of metalloradical catalysis (MRC) for controlling enantioselectivity as well as diastereoselectivity in radical cascade cyclization, we herein report the development of a Co(II)-based catalytic system for asymmetric radical bicyclization of 1,6-enynes with diazo compounds. Through the fine-tuning of D 2 -symmetric chiral amidoporphyrins as the supporting ligands, the Co(II)-catalyzed radical cascade process, which proceeds in a single operation under mild conditions, enables asymmetric construction of multisubstituted cyclopropane-fused tetrahydrofurans bearing three contiguous stereogenic centers, including two all-carbon quaternary centers, in high yields with excellent stereoselectivities. Combined computational and experimental studies have shed light on the underlying stepwise radical mechanism for this new Co(II)-based cascade bicyclization that involves the relay of several Co-supported C-centered radical intermediates, including α-, β-, γ-, and ε-metalloalkyl radicals. The resulting enantioenriched cyclopropane-fused tetrahydrofurans that contain a trisubstituted vinyl group at the bridgehead, as showcased in several stereospecific transformations, may serve as useful intermediates for stereoselective organic synthesis. The successful demonstration of this new asymmetric radical process via Co(II)-MRC points out a potentially general approach for controlling enantioselectivity as well as diastereoselectivity in synthetically attractive radical cascade reactions.

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Rhodium(i)-catalyzed vinylation/[2 + 1] carbocyclization of 1,6-enynes with α-diazocarbonyl compounds

Abstract: Rh(i)-catalyzed coupling–cyclization of enynes with diazo compounds has been developed to obtain versatile vinyl-substituted azabicyclo[3.1.0]hexanes.

Cited by 5 publications

References 55 publications

Recent Advances in Cyclization Reactions of 1,6‐Enynes

Recent Advances in Cyclization Reactions of 1,6‐Enynes

Expedient Synthesis of 6‐Functionalized Azabicyclo[4.1.0]heptane Derivatives

Controlling Enantioselectivity and Diastereoselectivity in Radical Cascade Cyclization for Construction of Bicyclic Structures

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