From gem‐Dichlorocyclobutenones to Cyclobutenols: Unveiling a Ruthenium‐Catalyzed Allylic Reduction‐Asymmetric Transfer Hydrogenation Cascade DOI
Christophe Meyer,

Olivier Charron,

Marharyta Kosiuha

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 28, 2024

Abstract Cyclobutenones constitute an appealing class of substrates in catalytic asymmetric transformations leading to diversely substituted enantioenriched four‐membered carbocycles, which are eliciting a growing interest medicinal chemistry. Whilst several synthetically useful enantioselective conjugate addition reactions have been reported, the reduction carbonyl group simple cyclobutenones remains elusive transformation. Herein, we disclose discovery novel allylic reduction‐asymmetric transfer hydrogenation cascade, catalyzed by Noyori‐Ikariya ruthenium complex, from readily available gem ‐dichlorocyclobutenones, 2‐chlorocyclobutenols with high optical purities, can be engaged postfunctionalization enabling access rings.

Язык: Английский

Sc-Catalyzed Asymmetric [2 + 2] Annulation of 2-Alkynylnaphthols with Dienes to Access Cyclobutene Frameworks DOI
Ke Xu, Heping Li,

Yan‐Ling Ji

и другие.

Organic Letters, Год журнала: 2025, Номер 27(4), С. 1006 - 1011

Опубликована: Янв. 16, 2025

Herein, we introduce a scandium-catalyzed synthetic strategy that provides access to diverse and functionalized array of cyclobutene frameworks adorned with quaternary carbon center. This approach broadens the repertoire 2-alkynylnaphthols alkenes, offering versatile platform for construction complex molecular architectures. The asymmetric catalytic [2 + 2] cycloaddition reaction demonstrates wide substrate scope an impressive functional group tolerance, yielding products high efficiency, up 97% yield, excellent enantiomeric excess 97%. simplicity scaling this process, coupled ease converting these into variety substituted products, significantly enhances utility method.

Язык: Английский

Процитировано

0
Stereoselective Alkyne–Alkene [2 + 2] Cycloaddition Enabled by Anion Relay Chemistry for Fully C-Substituted Cyclobutene Synthesis DOI

Xiaomeng Gong,

Ruipeng Li, Xiang‐Rong Xu

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 6, 2025

Cyclobutenes serve as valuable scaffolds in pharmaceutical development, but synthesizing structurally diverse fully C-substituted cyclobutenes remains challenging. Here we report a stereoselective [2 + 2] cycloaddition between alkynyl 1,3-dithianes and cinnamate esters using catalytic amount of KOtBu. Our approach enables the construction synthetically challenging tetrasubstituted via anion relay chemistry (ARC), exhibiting excellent trans-diastereoselectivities (dr > 20:1).

Язык: Английский

Процитировано

0
Phosphoric Acid-Catalyzed Enantioselective Synthesis of Axially Chiral Cyclobutanamides DOI

Guang Cheng,

Jinfeng Zheng,

Yilin Zhu

и другие.

Organic Letters, Год журнала: 2025, Номер 27(10), С. 2509 - 2514

Опубликована: Март 5, 2025

Chiral cyclobutanamide is a privileged scaffold in drug discovery. Here, we describe, for the first time, synthesis of axially chiral cyclobutanamides via phosphoric acid-catalyzed enantioselective condensation between N-arylcarbamyl cyclobutanones and hydroxylamines. Rational substrate design, incorporating an amide moiety (CONHR) into cyclobutanone backbone formation multi-hydrogen bonding network involving N-H this portion, responsible excellent enantioselectivity achieved stereodetermining dehydration process, which supported by detailed mechanistic study.

Язык: Английский

Процитировано

0
Catalytic Schmittel-Type [2+2] Cycloaddition of γ-Alkynyl Diazoacetates with Terminal Alkynes for Accessing Cyclobuta[a]indenes DOI
Wei Hao, Yan Zhang,

Nan-Nan Wang

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 17, 2025

Instead of the conventional [4+2] cycloaddition, a regioselective Schmittel-type [2+2] cycloaddition yne–allene esters, generated in situ from copper-catalyzed dediazotized coupling γ-alkynyl diazoacetates with terminal alkynes, is reported, enabling bicyclization process to produce diverse array C1-arylated cyclobuta[a]indenes moderate good yields. The protocol features wide functional group compatibility, mild reaction conditions, and experimental simplicity, holding significant potential for building new tricyclic cyclobutenes.

Язык: Английский

Процитировано

0
Photoredox cobalt-catalyzed asymmetric desymmetric reductive coupling of cyclobutenes with alkynes DOI Creative Commons

Tianlong Zeng,

Yezeng He, Ying Li

и другие.

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 1, 2025

Catalytic methods to couple alkynes and alkenes are highly valuable in synthetic chemistry. The cobalt-catalyzed intermolecular reductive coupling of is particularly attractive due the unique reactivity cost-effectiveness cobalt catalysts. However, enantioselective transformations this kind less developed. limited successful examples restricted use electronically biased activated olefins as partners. Herein, we report an asymmetric desymmetric unbiased succinimide-containing cyclobutenes with synthesize enantioenriched, synthetically important vinyl cyclobutanes via photoredox dual catalysis. Excellent enantioselectivities, good diastereoselectivities regioselectivities obtained. Preliminary mechanistic studies suggest that Hantzsch ester a better reducing reagent when used combination Et3N. Density functional theory calculations reveal reaction proceeds more likely through Co(III)-H migratory insertion mechanism. Here, authors internal

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

1
Palladium-Catalyzed Regio- and Diastereoselective Hydro(hetero)arylation for Rapid Construction of Quaternary Center Containing Cyclobutanes DOI
Furong Tao,

Shuaikang Li,

Mandalaparthi Phanindrudu

и другие.

Organic Letters, Год журнала: 2024, Номер 26(34), С. 7222 - 7226

Опубликована: Авг. 19, 2024

Herein we report a Pd-catalyzed regio- and diastereoselective hydro(hetero)arylation of inactivated alkylidenecyclobutanes. This protocol provides rapid atom-economical route to access 3-cyclobutyl (hetero)arenes with good functionalities toleration. With the assistance directing group, nucleophilic attack happened on bulkier γ-position form quaternary carbon center. Furthermore, selected products exhibited antitumor bioactivities.

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, 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

0
From gem‐Dichlorocyclobutenones to Cyclobutenols: Unveiling a Ruthenium‐Catalyzed Allylic Reduction‐Asymmetric Transfer Hydrogenation Cascade DOI
Christophe Meyer,

Olivier Charron,

Marharyta Kosiuha

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 28, 2024

Abstract Cyclobutenones constitute an appealing class of substrates in catalytic asymmetric transformations leading to diversely substituted enantioenriched four‐membered carbocycles, which are eliciting a growing interest medicinal chemistry. Whilst several synthetically useful enantioselective conjugate addition reactions have been reported, the reduction carbonyl group simple cyclobutenones remains elusive transformation. Herein, we disclose discovery novel allylic reduction‐asymmetric transfer hydrogenation cascade, catalyzed by Noyori‐Ikariya ruthenium complex, from readily available gem ‐dichlorocyclobutenones, 2‐chlorocyclobutenols with high optical purities, can be engaged postfunctionalization enabling access rings.

Язык: Английский

Процитировано

0