Access to Alkenyl Cyclobutanols by Ni‐Catalyzed Regio‐ and Enantio‐selective syn‐Hydrometalative 4‐exo‐trig Cyclization of Alkynones DOI
Xiaolin Li,

Jiang-Lian Deng,

Jian Long

и другие.

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Окт. 12, 2024

Abstract Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel‐catalyzed asymmetric syn ‐hydrometalative 4‐ exo ‐ trig cyclization 1,4‐alkynones to synthesize alkenyl cyclobutanols with tetrasubstituted stereocenter. This strategy features broad substrate scope, delivering variety trifluoromethyl‐containing rigid (spiro)carbocycle skeletons in good yields high enantioselectivities (up 84 % yield 98.5 : 1.5 er). The utility is demonstrated through stereospecific transformations into fused spiro molecules. Experimental computational mechanistic studies indicate that the reaction initiated by an active Ni−H species, carbonyl‐directed hydrometalation as key regioselective control. catalytic method provides general solution hydrofunctionalization alkynes represents efficient pattern assembling highly strained enantioenriched bioisosteres.

Язык: Английский

Synthesis of 2‐Azanorbornanes via Strain‐Release Formal Cycloadditions Initiated by Energy Transfer DOI Creative Commons

Yu‐Che Chang,

Christophe Salomé, Thomas C. Fessard

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(51)

Опубликована: Ноя. 14, 2023

Rigid bicycles are becoming more popular in the pharmaceutical industry because they allow for expansion to new and unique chemical spaces. This work describes a strategy construct 2-azanorbornanes, which can act as rigid piperidine/pyrrolidine scaffolds with well-defined exit vectors. To achieve synthesis of strain-release reagent, azahousane, is introduced along its photosensitized formal cycloaddition alkenes. Furthermore, reactivity between housane an imine disclosed. Both strategies lead various substituted 2-azanorbornanes good selectivities.

Язык: Английский

Процитировано

20

General Alkene 1,2-syn-Cyano-Hydroxylation Procedure Via Electrochemical Activation of Isoxazoline Cycloadducts DOI Creative Commons

Taciano A. S. Wanderley,

Roberto Buscemi,

Órla Conboy

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(47), С. 32848 - 32858

Опубликована: Ноя. 13, 2024

Stereoselective alkene 1,2-difunctionalization is a privileged strategy to access three-dimensional C(sp

Язык: Английский

Процитировано

3

An unconventional photochemical tetrahydroisoquinoline synthesis from sulfonylimines and alkenes DOI

Wang Wang,

Bei Zhao, Xiaotian Qi

и другие.

Chem, Год журнала: 2025, Номер unknown, С. 102488 - 102488

Опубликована: Март 1, 2025

Язык: Английский

Процитировано

0

Photoinduced Formal Cross-[3+3] Cycloaddition of Vinyldiazo Reagents with Acceptor-Only Diazoalkanes DOI
Yang Xie, Lihua Zhang, Jun Xuan

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 22, 2025

In this study, we devised an innovative approach for the synthesis of pyrazine derivatives through a photoinduced formal cross-[3+3] cycloaddition between vinyldiazo reagents and acceptor-only diazoalkanes. This method leverages differential reactivity two distinct diazo compounds: reagents, which upon visible light irradiation form key cyclopropane intermediates, diazoalkanes, function as 1,3-dipoles to capture photogenerated reactive species. The reactions proceed exclusively under light, yielding 1,4-dihydropyridazines with broad substrate scope compatibility various functional groups. Importantly, synthesized can be readily converted other valuable products. mechanism, elucidated UV–vis absorption studies, deuterium labeling experiments, control in situ NMR spectroscopy, provides clear understanding observed reactivity.

Язык: Английский

Процитировано

0

Photochemical Dual Radical Coupling of Carboxylates with Alkenes/Heteroarenes via Diradical Equivalents DOI
Guanjie Wang,

Jingxin Ding,

J. Wu

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 24, 2025

Carboxylate diradical intermediates, with α-carbon and carboxylic oxygen acting as reactive radical centers, represent a highly attractive long-sought species in reaction design synthesis. However, capturing these intermediates for coupling reactions poses formidable challenge due to their inherent instability spontaneous decarboxylation. Here, we addressed this by temporarily masking the carboxylate reactivity via photocleavable dynamic oxygen–iodine bond. This approach effectively prevents unwanted decarboxylation enables controlled utilization of forming new bonds. Carboxylates alkenes/heteroarenes, among most readily available raw materials, can now seamlessly couple pathways form γ-butyrolactones, which are common motifs found numerous natural products bioactive molecules. Ionic traditional carboxylates ruled out based on experimental studies density functional theory (DFT) calculations. strategy overcomes substrate limitations methods, significantly expanding range applicable alkenes/heteroarenes. Our method allows transforming alkenes modes diverse offers insights into developing di- multiradical equivalents unprecedented synthetic designs.

Язык: Английский

Процитировано

0

Efficient and selective energy transfer photoenzymes powered by visible light DOI Creative Commons
Rebecca Crawshaw, Ross Smithson, Johannes Hofer

и другие.

Nature Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 6, 2025

Abstract The development of [2 + 2] cyclases containing benzophenone triplet sensitizers highlights the potential engineered enzymes as a platform for stereocontrolled energy transfer photocatalysis. However, suboptimal photophysical features necessitates use ultraviolet light, limits photochemical efficiency and restricts range chemistries accessible. Here we engineer an orthogonal Methanococcus jannaschii tyrosyl-tRNA synthetase/tRNA pair encoding thioxanthone into proteins, which can efficiently harness visible light to drive conversions. Initially, developed enantioselective cyclase that is orders magnitude more efficient than our previously photoenzymes ( k cat = 13 s −1 , >1,300 turnovers). To demonstrate thioxanthone-containing enable challenging conversions, second oxygen-tolerant enzyme steer selective C–H insertions excited quinolone substrates afford spirocyclic β-lactams with high selectivity (99% e.e., 22:1 d.r.). This photoenzyme also suppresses competing substrate decomposition pathway observed small-molecule sensitizers, underscoring ability control fate excited-state intermediates.

Язык: Английский

Процитировано

0

Organocatalyzed Asymmetric [2+2] Cycloaddition of Saccharin-Derived Endocyclic Ketimines and Allenoates for the Synthesis of Fused Azetidines DOI Creative Commons

Xinyu Liu,

Yunfeng Zhang,

Luning Zhou

и другие.

Tetrahedron Chem, Год журнала: 2025, Номер 14, С. 100133 - 100133

Опубликована: Май 10, 2025

Язык: Английский

Процитировано

0

[2 + 2] Photocycloadditions of Conformationally Constrained Styrenes Enabled by Triplet Lifetime Extension DOI

Christina Cong,

Nicholas J. Fastuca, Alberto Castanedo

и другие.

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

Опубликована: Июнь 3, 2025

We report an intermolecular, cross-selective [2 + 2] cycloaddition between cyclic styrenes and olefin acceptors proceeding via visible-light irradiation, enabled by the extended triplet lifetime of styrenes. A broad range olefins, including electron-deficient simple alkenes, (hetero)styrenes, arylimines, vinyl boronate esters, among others, underwent efficient with constrained four-, five-, rigidified six-membered rings, providing rapid access to sp3-rich fused cyclobutane scaffolds. Notably, two electronically similar styrenes, which typically gives statistical mixtures homo- heterodimers, proceeded excellent chemoselectivity yield acyclic without requiring a large excess one reactant, facilitated significant difference in reacting partners. Mechanistic studies DFT calculations support Dexter energy transfer mechanism substrate activation underscore critical role extension enabling observed reactivity. The utility this method is demonstrated total synthesis lindleyanin, only steps.

Язык: Английский

Процитировано

0

Access to Alkenyl Cyclobutanols by Ni‐Catalyzed Regio‐ and Enantio‐selective syn‐Hydrometalative 4‐exo‐trig Cyclization of Alkynones DOI
Xiaolin Li,

Jiang-Lian Deng,

Jian Long

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Окт. 12, 2024

Abstract Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel‐catalyzed asymmetric syn ‐hydrometalative 4‐ exo ‐ trig cyclization 1,4‐alkynones to synthesize alkenyl cyclobutanols with tetrasubstituted stereocenter. This strategy features broad substrate scope, delivering variety trifluoromethyl‐containing rigid (spiro)carbocycle skeletons in good yields high enantioselectivities (up 84 % yield 98.5 : 1.5 er). The utility is demonstrated through stereospecific transformations into fused spiro molecules. Experimental computational mechanistic studies indicate that the reaction initiated by an active Ni−H species, carbonyl‐directed hydrometalation as key regioselective control. catalytic method provides general solution hydrofunctionalization alkynes represents efficient pattern assembling highly strained enantioenriched bioisosteres.

Язык: Английский

Процитировано

2

Catalytic Asymmetric Reactions of Ketimines and Alkenes via [2 + 2] Cycloaddition: Chemical Reactivity Controlled by Switching a Heteroatom DOI
Qun Zhao, Yao Li, Zhiyuan Ren

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(46), С. 32088 - 32097

Опубликована: Ноя. 8, 2024

Azetidine units are commonly found in natural products and biologically active drugs. The [2 + 2] cycloaddition of imines alkenes has been extensively used the synthesis such structures, while enantioselective approaches remain elusive. Herein, an efficient B(C

Язык: Английский

Процитировано

2