Stereodivergent, Multicomponent Metal-Catalyzed Couplings Generating Three Stereocenters: Combining Enantioselective Rh-Catalyzed Conjugate Addition and Ir-Catalyzed Allylic Alkylation DOI Creative Commons

Qiqige Qiqige,

Rylan J. Lundgren, Duanyang Kong

и другие.

Опубликована: Ноя. 4, 2022

Stereodivergent dual catalysis has emerged as a powerful tool to selectively prepare all four stereoisomers in molecules containing two chiral centers from common starting materials. Most processes involve the use of substrates, and it remains challenging catalyst approaches generate having three newly formed stereocenters with high diastereo- enantioselectivity. Here we report multicomponent, stereodivergent method for synthesis targets contiguous by combination enantioselective Rh-catalyzed conjugate addition Ir-catalyzed allylic alkylation methodologies. Both cyclic acyclic ,-unsaturated ketones undergo -arylation using aryl boron reagents form an enolate nucleophile that can be subsequently allylated at -position. The reactions proceed generally >95% ee >90:10 dr. Epimerization -carbonyl center enables preparation any eight possible materials, demonstrated cyclohexanone products.

Язык: Английский

Stereodivergent Construction of 1,3‐Chiral Centers via Tandem Asymmetric Conjugate Addition and Allylic Substitution Reaction DOI
Jiahao Xie,

Yi‐Ming Hou,

Zuolijun Feng

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(10)

Опубликована: Янв. 4, 2023

Herein, we report a synthesis of cyclohexanones bearing multi-continuous stereocenters by combining copper-catalyzed asymmetric conjugate addition dialkylzinc reagents to cyclic enones with iridium-catalyzed allylic substitution reaction. Good excellent yields, diastereoselectivity and enantioselectivity can be obtained. Unlike the stereodivergent construction adjacent (1,2-position) reported in literature, current reaction achieve nonadjacent (1,3-position) proper combination two chiral catalysts different enantiomers.

Язык: Английский

Процитировано

34
Ir‐Catalyzed Enantioselective Synthesis of gem‐Diborylalkenes Enabled by 1,2‐Boron Shift DOI

Jianfei Ge,

Xi‐Zhang Zou,

Xinru Liu

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)

Опубликована: Июнь 15, 2023

Abstract Asymmetric cross‐couplings based on 1,2‐carbon migration from B‐ate complexes have been developed efficiently to access valuable organoboronates. However, enantioselective reactions triggered by 1,2‐boron shift remained be unaddressed synthetic challenge. Here, Ir‐catalyzed asymmetric allylic alkylation enabled was developed. In this reaction, we disclosed that excellent enantioselectivities were achieved through an interesting dynamic kinetic resolution (DKR) process of carbonates at the elevated temperature. Notably, highly (bis‐boryl)alkenes array diversifications versatile molecules. Extensive experimental and computational studies conducted elucidate reaction mechanism DKR clarify origin enantioselectivities.

Язык: Английский

Процитировано

27
Photoredox cobalt-catalyzed regio-, diastereo- and enantioselective propargylation of aldehydes via propargyl radicals DOI Creative Commons
Lei Wang,

Chuiyi Lin,

Qinglei Chong

и другие.

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Авг. 10, 2023

Catalytic enantioselective introduction of a propargyl group constitutes one the most important carbon-carbon forming reactions, as it is versatile to be transformed into diverse functional groups and frequently used in synthesis natural products biologically active molecules. Stereoconvergent transformations racemic precursors single enantiomer via radicals represent powerful strategy provide new reactivity. However, only few Cu- or Ni-catalyzed protocols have been developed with limited reaction modes. Herein, photoredox/cobalt-catalyzed regio-, diastereo- addition aldehydes presented, enabling construction broad scope homopropargyl alcohols that are otherwise difficult access high efficiency stereoselectivity from carbonates. Mechanistic studies DFT calculations provided evidence for involvement radicals, origin stereoconvergent process stereochemical models.

Язык: Английский

Процитировано

20
Enantioselective and Regiodivergent Synthesis of Propargyl‐ and Allenylsilanes through Catalytic Propargylic C−H Deprotonation DOI Creative Commons
Jin Zhu,

Hengye Xiang,

Hai Won Chang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(16)

Опубликована: Фев. 13, 2024

Abstract We report a highly enantioselective intermolecular C−H bond silylation catalyzed by phosphoramidite‐ligated iridium catalyst. Under reagent‐controlled protocols, propargylsilanes resulting from C(sp 3 )−H functionalization, as well the regioisomeric and synthetically versatile allenylsilanes, could be obtained with excellent levels of enantioselectivity good to control propargyl/allenyl selectivity. In case unsymmetrical dialkyl acetylenes, selectivity for functionalization at less‐hindered site was also observed. A variety electrophilic silyl sources (R SiOTf R SiNTf 2 ), either commercial or in situ ‐ generated, were used reagents, broad range simple functionalized alkynes, including aryl alkyl 1,3‐enynes, drug derivatives successfully employed substrates. Detailed mechanistic experiments DFT calculations suggest that an η ‐propargyl/allenyl Ir intermediate is generated upon π‐complexation‐assisted deprotonation undergoes outer‐sphere attack silylating reagent give propargylic silanes, latter step identified enantiodetermining step.

Язык: Английский

Процитировано

7
A C–H functionalization approach to diverse nitrogenous scaffolds through conjugate addition of catalytic allyliron nucleophiles DOI Creative Commons

Sarah G. Scrivener,

Yiming Wang

Chemical Science, Год журнала: 2024, Номер 15(23), С. 8850 - 8857

Опубликована: Янв. 1, 2024

Cyclopentadienyliron( ii ) dicarbonyl complexes capable of coordinating to and enhancing the acidity a range unsaturated substrates have emerged as new class base-metal derived catalysts for C–H functionalization.

Язык: Английский

Процитировано

5
Palladium-catalyzed allylation and carbonylation: access to allylhydrazones and allyl acylhydrazones DOI

Qianqian Liang,

Yan Cai,

Wenjun Jiang

и другие.

Chemical Communications, Год журнала: 2024, Номер 60(12), С. 1638 - 1641

Опубликована: Янв. 1, 2024

A practical one-pot catalytic tandem multicomponent allylation condensation carbonylation to construct allylhydrazones and allyl acylhydrazones with high atom economy, water as a coproduct excellent regioselectivity in reactions.

Язык: Английский

Процитировано

4
Transition Metal Mimetic π-Activation by Cationic Bismuth(III) Catalysts for Allylic C–H Functionalization of Olefins Using C═O and C═N Electrophiles DOI Creative Commons

Ruihan Wang,

Sebastián Martínez,

Johannes Schwarzmann

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22122 - 22128

Опубликована: Авг. 5, 2024

The discovery and utilization of main-group element catalysts that behave similarly to transition metal (TM) complexes have become increasingly active areas investigation in recent years. Here, we report a series Lewis acidic bismuth(III) allow for the catalytic allylic C(sp3)–H functionalization olefins via an organometallic complexation-assisted deprotonation mechanism generate products containing new C–C bonds. This heretofore unexplored mode reactivity was applied regioselective 1,4-dienes allylbenzene substrates. Experimental computational mechanistic studies support key steps proposed cycle, including intermediacy elusive Bi–olefin allylbismuth species.

Язык: Английский

Процитировано

2
Stereodivergent Construction of 1,3‐Chiral Centers via Tandem Asymmetric Conjugate Addition and Allylic Substitution Reaction DOI
Jiahao Xie,

Yi‐Ming Hou,

Zuolijun Feng

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 135(10)

Опубликована: Янв. 4, 2023

Abstract Herein, we report a synthesis of cyclohexanones bearing multi‐continuous stereocenters by combining copper‐catalyzed asymmetric conjugate addition dialkylzinc reagents to cyclic enones with iridium‐catalyzed allylic substitution reaction. Good excellent yields, diastereoselectivity and enantioselectivity can be obtained. Unlike the stereodivergent construction adjacent (1,2‐position) reported in literature, current reaction achieve nonadjacent (1,3‐position) proper combination two chiral catalysts different enantiomers.

Язык: Английский

Процитировано

4
Copper-catalyzed propargylic C–H functionalization for allene syntheses DOI Creative Commons
Dongjie Zhang, Junjie Fan,

Yaqi Shi

и другие.

Chemical Science, Год журнала: 2023, Номер 14(34), С. 9191 - 9196

Опубликована: Янв. 1, 2023

Allenenitriles bearing different synthetically versatile functional groups have been prepared smoothly from 5-alkynyl fluorosulfonamides in decent yields with an excellent chemo- and regio-selectivity under redox neutral conditions. The resulting allenenitriles can be readily converted to useful functionalized heterocycles. Based on mechanistic study, it is confirmed that this the first example of radical-based non-activated propargylic C-H functionalization for allene syntheses.

Язык: Английский

Процитировано

4
Enantioselective and Regiodivergent Synthesis of Propargyl‐ and Allenylsilanes through Catalytic Propargylic C−H Deprotonation DOI
Jin Zhu,

Hengye Xiang,

Hai Won Chang

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(16)

Опубликована: Фев. 13, 2024

Abstract We report a highly enantioselective intermolecular C−H bond silylation catalyzed by phosphoramidite‐ligated iridium catalyst. Under reagent‐controlled protocols, propargylsilanes resulting from C(sp 3 )−H functionalization, as well the regioisomeric and synthetically versatile allenylsilanes, could be obtained with excellent levels of enantioselectivity good to control propargyl/allenyl selectivity. In case unsymmetrical dialkyl acetylenes, selectivity for functionalization at less‐hindered site was also observed. A variety electrophilic silyl sources (R SiOTf R SiNTf 2 ), either commercial or in situ ‐ generated, were used reagents, broad range simple functionalized alkynes, including aryl alkyl 1,3‐enynes, drug derivatives successfully employed substrates. Detailed mechanistic experiments DFT calculations suggest that an η ‐propargyl/allenyl Ir intermediate is generated upon π‐complexation‐assisted deprotonation undergoes outer‐sphere attack silylating reagent give propargylic silanes, latter step identified enantiodetermining step.

Язык: Английский

Процитировано

1