Recent Advances in Cyclization Reactions of 1,6‐Enynes

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(6), С. 1220 - 1268

Опубликована: Янв. 22, 2024

Abstract 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 biologically active pharmaceutical molecules. Over the past few decades, development versatile synthetic approaches via cascade cyclization reactions 1,6‐enynes for construction a series fused spiro compounds has been focus great deal research initiatives. These synthesis strategies peculiarly fascinating context assembly wide array molecules, products, agrochemicals, functional materials. In this review, recent developments transformations with diverse coupling reagents summarized since 2018, which could be divided into five categories: 1) Introduction; 2) Transition metal catalyzed 1,6‐enynes; 3) Metal‐free 4) Visible‐light‐induced 5) Electrocatalytic 1,6‐enynes.

Язык: Английский

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Nickel-catalyzed switchable arylative/endo-cyclization of 1,6-enynes

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Апрель 4, 2024

Abstract Carbo- and heterocycles are frequently used as crucial scaffolds in natural products, fine chemicals, biologically pharmaceutically active compounds. Transition-metal-catalyzed cyclization of 1,6-enynes has emerged a powerful strategy for constructing functionalized carbo- heterocycles. Despite significant progress, the regioselectivity alkyne functionalization is entirely substrate-dependent. And only exo -cyclization/cross-coupling products can be obtained, while endo -selective cyclization/cross-coupling remains elusive still poses formidable challenge. In this study, we disclose nickel-catalyzed switchable arylation/cyclization which nature ligand dictates arylation, electrophilic trapping reagents determine selectivity mode. Specifically, using commercially available 1,10-phenanthroline facilitates trans -arylation/cyclization to obtain seven-membered ring 2-naphthyl-substituted bisbox promotes cis access six-membered products. Diastereoselective cyclizations have also been developed synthesis enantioenriched piperidines azepanes, core structural elements pharmaceuticals possessing important biological activities. Furthermore, experimental density functional theory studies reveal that arylation process controlled by steric hindrance ligand; reaction mechanism involves -cyclization followed Dowd-Beckwith-type expansion form

Язык: Английский

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Photoinduced arylative formal 4-endo-dig cyclization of propargyl alcohols/amines to access strained heterocycles

Green Chemistry, Год журнала: 2024, Номер 26(5), С. 2705 - 2711

Опубликована: Янв. 1, 2024

A novel synthetic strategy to access strained heterocycles is revealed through photocatalysed annulative formal 4- endo-dig cyclization of propargyl alcohols/amines with benzoquinones under catalyst/reagent-free conditions using non-hazardous solvent.

Язык: Английский

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Rhodium‐Catalyzed Dual C−H Activation for Regioselective Triple Annulation of Enaminones: Access to Polycyclic Naphthopyran Derivatives

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(11), С. 1770 - 1776

Опубликована: Март 21, 2023

Abstract Rh‐catalyzed C−H activation of arenes for oxidative annulations with alkynes stands out as a protocol polycyclic scaffolds. This perspective drives us to disclose herein rhodium catalyzed regioselective triple annulation enaminones hydroxyl‐alkynoates via double functionalization naphtho‐pyran Secondary coordination OH in alkynoate dictated the regioselectivity. Initial lactonization occurred chemoselectively on enamine part carbo rhodation followed by reductive elimination. was scalable and has shown high functionality tolerance. KIE studies were done get insight mechanism, some downstream transformations achieved show synthetic potential method.

Язык: Английский

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Pd-Catalyzed Selective Arylative Cascade Cyclization of 1,6-Diynes and Dibenzoxaborins for Fused Naphthalene Derivatives

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

A palladium-catalyzed new mode of cascade arylative cyclization 1,6-diynes is disclosed using dibenzoxaborin as an arylating agent featuring transmetalation and selective migratory insertion the key steps. This process enables efficient construction polysubstituted fused naphthalene skeletons via formation three C-C bonds through dual regioselectivity in both arylation well C-H functionalization. Some control experiments kinetic isotope effect (KIE) studies were conducted to elucidate reaction mechanism, some product diversifications achieved showcase synthetic potential.

Язык: Английский

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Rhodium-Catalyzed Coordination-Assisted Regioselective and Migratory Three-Point Double Annulation of o-Alkenyl Phenols with Tertiary Propargyl Alcohols

Organic Letters, Год журнала: 2022, Номер 24(28), С. 5062 - 5067

Опубликована: Июль 11, 2022

We disclose herein a Rh(III)-catalyzed migratory three-point double annulation of o-alkenyl phenols with propargyl alcohols for de novo construction naphtho furan derivatives in regio- and chemoselective manner. The protocol orchestrates two new rings four bonds one operation without the need any additive. Necessary labeled control experiments are conducted to elucidate reaction mechanism. A tertiary hydroxyl group is found be crucial both controlling regioselective insertion alkyne through chelation rhodium form key spiro cyclic intermediate forcing ring expansion via unusual selective olefin reshuffling, apart from forming an extra (furan) ring. scalable shows tolerance late stage functionalization natural products.

Язык: Английский

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Highly efficient and fast synthesis of di-iodinated succinimide derivatives from 1,6-enyne and I₂ under air at room temperature

Green Chemistry, Год журнала: 2022, Номер 24(20), С. 8021 - 8028

Опубликована: Янв. 1, 2022

A metal-free, additive-free, and practical method for the synthesis of diiodinated succinimide derivatives has been achieved under mild conditions.

Язык: Английский

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Recent developments in nickel-catalyzed asymmetric cyclization and cycloaddition of carbonyl-alkynes, cyano-alkynes, and enynes

Chemical Communications, Год журнала: 2023, Номер 59(30), С. 4405 - 4422

Опубликована: Янв. 1, 2023

Alkynes as unsaturated hydrocarbons have long been used for cyclization reactions. Various transition metal-catalyzed cyclizations of alkynes reported in the past decades. In this minireview, we mainly summarize recent asymmetric with other functional groups such carbonyl-alkynes, cyano-alkynes, and enynes under catalytic system nickel chiral ligands.

Язык: Английский

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Recent advances in sulfur/sulfonyl radical triggered cascade cyclization reactions of 1,n-enynes

Tetrahedron, Год журнала: 2023, Номер 138, С. 133409 - 133409

Опубликована: Апрель 7, 2023

Язык: Английский

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Cu-Catalyzed tandem cyclization and coupling of enynones with enaminones for multisubstituted furans & furano-pyrroles

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(32), С. 6363 - 6367

Опубликована: Янв. 1, 2022

A cascade reaction of enynones with enaminones via cyclative coupling to engineer diverse multisubstituted furans and furano-pyrrole bisheterocycles is described proposed involve carbene insertion C–C migrations deliver a totally rearranged product.

Язык: Английский

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