Nickel-catalysed regio- and stereoselective acylzincation of unsaturated hydrocarbons with organozincs and CO

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(3), P. 261 - 274

Published: Jan. 5, 2023

Language: Английский

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Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

Beilstein Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 19, P. 487 - 540

Published: April 24, 2023

This review presents a comprehensive overview of transition-metal-catalyzed domino reactions strained bicyclic alkenes, including both homo- and heterobicyclic alkenes. These compounds are important synthons in organic synthesis, providing an platform for the construction biologically/medicinally significant which bear multiple stereocenters. The has been divided according to metal used reaction. An substrate scope, reaction conditions, their potential applications synthesis is discussed. A outlook on reactivity paradigms alkenes discussed should shed light future directions further development this field.

Language: Английский

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Recent Advances in the Cascade Cyclization Reactions of 1,7‐Enynes

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(3), P. 324 - 356

Published: Dec. 14, 2023

Abstract Elaborated molecular architectures, especially carbocyclic, heterocyclic, endocyclic, and polycyclic structures, serve as an important class of organic complexes because they are frequently occurring core structural units in a variety biologically pharmacologically relevant natural products, drug molecules, agrochemicals, functional materials. A main challenge current synthetic approaches is the development strategically efficient selective formation these compounds from easy‐to‐handle starting The cascade cyclizations 1,7‐enynes have afforded indispensable method for accessing complexity diversity, thus highlighting their potential significance both academic industrial communities. In last decades, tremendous efforts been devoted to discovering convenient routes access sophisticated annulation derivatives, wide range powerful straightforward strategies reported. this review, latest achievements cyclization reactions summarized, which could be separated into three categories: (1) Visible‐light‐induced 1,7‐enynes; (2) Metal‐free catalyzed (3) Transition‐metal‐catalyzed 1,7‐enynes.

Language: Английский

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Nickel(II)/Salox-Catalyzed Enantioselective C–H Functionalization

ACS Central Science, Journal Year: 2025, Volume and Issue: 11(1), P. 127 - 135

Published: Jan. 2, 2025

Recently, nickel catalysts have garnered considerable attention for their efficacy and versatility in asymmetric catalysis, attributed to distinctive properties. However, the use of cost-effective sustainable divalent C–H activation/asymmetric alkene insertion poses significant challenges due intricate control stereochemistry transformation tetracoordinate C–Ni(II) intermediate. Herein, we report a Ni(II)-catalyzed enantioselective C–H/N–H annulation with oxabicyclic alkenes. This protocol offers straightforward access chiral [2,2,1]-bridged bicyclic compounds bearing four consecutive stereocenters high enantioselectivity (up 96% ee). The development sterically hindered salicyloxazoline (Salox) ligand, TMS-Salox, is key success this protocol. Mechanistic investigations unveiled that Ni(III)-metalacyclic intermediate was formed through situ oxidation achiral organometallic Ni(II) species coordination Salox ligand. process led creation tailored pocket guides approach alkenes, thereby influencing determining stereochemistry.

Language: Английский

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Reimagining Dearomatization: Arenophile-Mediated Single-Atom Insertions and π-Extensions

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

ConspectusDearomatization of simple aromatics serves as one the most direct strategies for converting abundant chemical feedstocks into three-dimensional value-added products. Among such transformations, cycloadditions between arenes and alkenes have historically offered effective means to construct complex polycyclic architectures. However, traditionally harsh conditions, high-energy UV light irradiation, greatly limited scope this transformation. Nevertheless, recent progress has led development visible-light-promoted dearomative photocycloadditions with expanded capable preparing bicyclic structures.A fundamentally distinct approach involves visible-light activation arenophiles, which undergo para-photocycloaddition various aromatic compounds produce arene-arenophile cycloadducts. While only transiently stable subject retro-cycloaddition, further functionalization photocycloadducts allowed a wide collection dearomatization methodologies that access products orthogonal existing biological processes. Central strategy was observation photocycloaddition reveals π-system can be functionalized through traditional olefin chemistry. Coupled subsequent [4 + 2]-cycloreversion arenophile, process acts effectively isolate single from an ring. We developed several transformations bias methodology perform single-atom insertion π-extension reactions prepare unique cannot prepared easily means.Through application epoxidation, we were able develop method epoxidation pyridines arene-oxides pyridine-oxides, respectively. Notably, when arenophile chemistry is applied arenes, transposed site native olefinic reactivity, enabling site-selectivity functionalization. As result, oxygen (aza)arenes 3-benzoxepines. When applying in context cyclopropanations, accomplish cyclopropanation yield benzocycloheptatrienes upon cycloreversion. while Buchner ring expansion powerful carbon corresponding does not ring-expanded Furthermore, could utilized synthesis novel nanographenes M-region annulative (M-APEX) reaction. Traditionally, methods rely on reactivity at K- bay-region. arenophiles activate reactivity. arenophile-mediated diarylation, followed by cycloreversion, deliver π-extended exclusive selectivity.

Language: Английский

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Asymmetric Multi-Atom Insertion of Esters via Rh-Catalyzed Ring Opening of Oxabicyclic Alkenes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Precise skeletal manipulation involving insertion, deletion, and replacement has garnered considerable attention within the synthetic chemistry community. Among these processes, multi-atom insertion reactions in acyclic compounds remain a formidable challenge, primarily due to low efficiency of fragment recapture after cleavage, which results from lack substrate-specific proximity during reconstruction stage. Here, we report an asymmetric reaction esters via Rh-catalyzed ring opening oxabicyclic alkenes, achieving excellent regio-, diastereo-, enantioselectivity. This approach enables efficient rapid construction molecular library with chiral hydroxy-dihydronaphthalene scaffold, showcasing atom-efficient reaction. Detailed density functional theory calculations reveal key mechanistic features stereoselectivity-determining model this transformation.

Language: Английский

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4.1 Arenophile-Mediated Photochemical Dearomative Functionalization

Published: Jan. 1, 2025

Abstract Dearomatizations have long been recognized as an important class of reactions, with significant progress achieved; however, the utilization simple and nonactivated arenes remains a challenging endeavor due to their inherent inertness difficulty achieving selective transformations. This review highlights emerging dearomatization approach that enables conversion such under mild conditions: arenophile-mediated photochemical dearomative functionalization. methodology provides efficient access alicyclic structures, offering both functional stereochemical complexity, including C—C, C—B, C—N, C—O, C—H bond formations. Applications in synthesis complex bioactive compounds are also presented demonstrate unique versatility this strategy.

Language: Английский

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Enantioselective Palladium(II)‐Catalyzed Desymmetrizative Coupling of 7‐Azabenzonorbornadienes with Alkynylanilines

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 9, 2023

A PdII -catalyzed, domino enantioselective desymmetrizative coupling of 7-azabenzonorbornadienes with alkynylanilines is disclosed herein. This operationally simple transformation generates three covalent bonds and two contiguous stereocenters excellent enantio- diastereo-selectivity. The resulting functionalized indole-dihydronaphthalene-amine conjugates served as an appealing platform to streamline the diversity-oriented synthesis (DOS) other valuable enantioenriched compounds. DFT calculations revealed that stabilizing non-covalent interactions contributed observed enantioselectivity.

Language: Английский

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Nickel-electrocatalyzed enantioselective C–H activations for chemo-divergence

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 16, 2024

Abstract Enantioselective electrocatalysis bears unique potential for the sustainable assembly of enantiomerically enriched molecules 1–7 . This approach allows electro-oxidative C–H activation to be performed paired hydrogen evolution reaction 8,9 While recent progress featured scarce transition metals with limited availability 10–17 , we, herein, reveal that Earth-abundant 3d transition-metal nickel is characterized by performance, while having high natural abundance 18 and reduced toxicity 19 Thereby, electrocatalytic enabled enantioselective desymmetrizations bicyclic alkenes, leading three-dimensional molecular building blocks multiple stereogenic elements 20 Here, ligand optimization was guided smart feature analysis enantioselectivity enhancement. The detailed mechanistic investigation experimental studies organometallic intermediates in conjunction computational identified key features design including non-covalent interactions 21,22 guarantee full selectivity control.

Language: Английский

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A Short Total Synthesis of Benzophenanthridine Alkaloids via a Rhodium(III)-Catalyzed C–H Ring-Opening Reaction

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(21), P. 14826 - 14843

Published: Sept. 28, 2021

The biologically important naturally available benzophenanthridines were prepared efficiently in three steps with overall good yields. A new synthetic methodology involving a rhodium(III) catalyzed redox-neutral ring-opening of 7-azabenzonorbornadienes aromatic aldoximes is developed to synthesize the target molecules. C–H reaction highly diastereoselective and compatible various sensitive functional group substituted as well 7-azabenzonorbornadienes. products transformed into 13,14-dehydrobenzo phenanthridine derivatives by HCl hydrolysis. Subsequently, 13,14-dehydrobenzophenanthridines converted benzophenanthridine alkaloids presence DDQ. possible mechanism was proposed for supported deuterium labeling studies.

Language: Английский

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