Asymmetric reductive arylation and alkenylation to access S-chirogenic sulfinamides DOI Creative Commons

Xiaowu Fang,

Longlong Xi, Minyan Wang

и другие.

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

Опубликована: Март 15, 2025

The study of the stereochemistry organic sulfur compounds has been ongoing for over a century, with S-chirogenic pharmacophores playing an essential role in drug discovery within bioscience and medicinal chemistry. Traditionally, synthesis sulfinamides featuring stereogenic sulfur(IV) centers involves complex, multistep process that often depends on chiral auxiliaries or kinetic resolution. Here, we introduce effective versatile method synthesizing diverse classes through selective aryl alkenyl addition to sulfinylamines. This is catalysed by nickel cobalt complex under reductive conditions, eliminating need preformed organometallic reagents. facilitates incorporation array halides at position, enabling their integration into various biologically significant pharmacophores. Our detailed mechanistic investigations density functional theory calculations provide insights reaction pathway, particularly highlighting enantiocontrol mode during process. play authors report methodology asymmetric sulfinylamines via common-Earth-metal catalysis.

Язык: Английский

Expedient Synthesis of Axially and Centrally Chiral Diaryl Ethers via Cobalt-Catalyzed Photoreductive Desymmetrization DOI
Yishou Wang,

Ruijie Mi,

Songjie Yu

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4638 - 4647

Опубликована: Март 12, 2024

Axially chiral diaryl ethers make up a unique class of atropisomers bearing restricted rotation about the C–O bond. Methods for expedient synthesis axially ether-based structures have been largely underdeveloped. Herein, we developed an efficient metal-catalyzed desymmetrization strategy to unveil formation and centrally dual in high diastereo- enantioselectivity. The protocol leverages cobalt-catalyzed photoreductive enantioselective couplings dialdehyde alkyne deliver stereogenicity, ether scaffold is equipped with useful synthetic handles including formyl, hydroxyl, allyl groups, as has demonstrated carboxylic acid potential ligand asymmetric catalysis.

Язык: Английский

Процитировано

16

Cobalt‐Catalyzed Enantioselective Reductive α‐Chloro‐Carbonyl Addition of Ketimine to Construct the β‐Tertiary Amino Acid Analogues DOI

Tingting Xia,

Wenwen Wu, Xianqing Wu

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)

Опубликована: Янв. 22, 2024

β-Tertiary amino acid derivatives constitute one of the most frequently occurring units in natural products and bioactive molecules. However, efficient asymmetric synthesis this motif still remains a significant challenge. Herein, we disclose cobalt-catalyzed enantioselective reductive addition reaction ketimine using α-chloro carbonyl compound as radical precursor, providing expedient access to diverse array enantioenriched β-quaternary analogues. This protocol exhibits outstanding enantioselectivity broad substrate scope with excellent functional group tolerance. Preliminary mechanism studies rule out possibility Reformatsky-type confirm involvement species stereoselective process. The synthetic utility has been demonstrated through rapid assembly iterative oligopeptide, showcasing its versatile platform for late-stage modification drug candidates.

Язык: Английский

Процитировано

14

Nickel-Catalyzed Enantioselective Reductive Arylation of Common Ketones DOI
Shuai Huang, Jianrong Steve Zhou

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(19), С. 12895 - 12900

Опубликована: Май 2, 2024

A nickel complex of chiral bisoxazolines catalyzed the stereoselective reductive arylation ketones in high enantioselectivity. range common acyclic and cyclic reacted without aid directing groups. Mechanistic studies using isolated a bis(oxazoline) (L)Ni(Ar)Br revealed that Mn reduction was not needed, while Lewis acidic titanium alkoxides were critical to ketone insertion.

Язык: Английский

Процитировано

11

Photocatalytic Deuterium Atom Transfer Deuteration of Electron‐Deficient Alkenes with High Functional Group Tolerance DOI
Akihiko Suzuki,

Yuji Kamei,

Masaaki Yamashita

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(3)

Опубликована: Ноя. 17, 2022

Abstract Due to its mild reaction conditions and unique chemoselectivity, hydrogen atom transfer (HAT) hydrogenation represents an indispensable method for the synthesis of complex molecules. Its analog using deuterium, deuterium (DAT) deuteration, is expected enable access deuterium‐labeled compounds. However, DAT deuteration has been scarcely studied synthetic purposes, a that possesses favorable characteristics HAT hydrogenations remained elusive. Herein, we report protocol photocatalytic electron‐deficient alkenes. In contrast previous this tolerates variety synthetically useful functional groups including haloarenes. The late‐stage also allows deuterated amino acids as well donepezil‐ d 2 . Thus, work demonstrates potential chemistry become alternative choice preparing deuterium‐containing

Язык: Английский

Процитировано

39

Selective Reductive Coupling of Vinyl Azaarenes and Alkynes via Photoredox Cobalt Dual Catalysis DOI
Zheng‐Yang Gu, Wen‐Duo Li,

Yan‐Lin Li

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(1)

Опубликована: Сен. 30, 2022

A visible light-induced Co-catalyzed highly regio- and stereoselective reductive coupling of vinyl azaarenes alkynes has been developed. Notably, Hünig's base together with simple ethanol successfully applied as the hydrogen sources instead commonly used Hantzsch esters in this catalytic photoredox reaction. This approach considerable advantages for straightforward synthesis stereodefined multiple substituted alkenes bearing an azaarene motif, such excellent regioselectivity (>20 : 1 >30 examples) stereoselectivity E/Z), broad substrate scope good functional group compatibility under mild reaction conditions, which utilized concise natural product monomorine I. reasonable pathway involving protolysis cobaltacyclopentene intermediate proposed based on mechanistic studies.

Язык: Английский

Процитировано

36

Nickel-Catalyzed Enantioselective Coupling of Acid Chlorides with α-Bromobenzoates: An Asymmetric Acyloin Synthesis DOI

Haiting Ji,

Dengkai Lin,

Lanzhu Tai

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(50), С. 23019 - 23029

Опубликована: Дек. 8, 2022

The reaction of common acyl-metal species (acyl anion) with aldehydes to furnish acyloins has received much less attention and specifically was restricted using preformed stoichiometric reagents. Moreover, the (catalytic) enantioselective variants remain unexplored, asymmetric synthesis chiral met significant challenges in organic synthesis. Here, we uncover highly coupling acid chlorides α-bromobenzoates by nickel catalysis for producing enantioenriched protected α-hydroxy ketones (acyloins, >60 examples) high enantioselectivities (up 99% ee). successful execution this protocol enables formation a key ketyl radical from α-bromoalkyl benzoate situ generated corresponding aldehyde acyl bromide, which finally is captured acyl-Ni catalytically formed chlorides, thus avoiding use synthetic utility chemistry demonstrated downstream elaboration toward diverse set synthetically valuable building blocks biologically active compounds.

Язык: Английский

Процитировано

31

Recent Advances in Nonprecious Metal Catalysis DOI
Michael C. Haibach, Shashank Shekhar, Tonia S. Ahmed

и другие.

Organic Process Research & Development, Год журнала: 2023, Номер 27(3), С. 423 - 447

Опубликована: Фев. 17, 2023

Nonprecious-metal-catalyzed alternatives to powerful precious metal transformations are of increasing interest in academia and the pharmaceutical industry due lower cost, better sustainability, toxicity. With continual growth broad field nonprecious catalysis (NPMC), we have chosen highlight selected articles published from March June 2022 which intended examples NPMC that feel may be especially relevant development. We aim inspire academic industrial innovation through discussion herein.

Язык: Английский

Процитировано

23

Enantioselective Reductive (Hetero)Arylation of Cyclic N‐Sulfonyl Imines by Cobalt Catalysis DOI

Jieshuai Xiao,

Minyan Wang,

Xuwen Yin

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(19)

Опубликована: Март 14, 2023

Transition-metal-catalyzed enantioselective addition of aryl organometallic reagents to imines has emerged as one the most powerful tools for formation optically active diarylmethylamines. Here, we report first asymmetric reductive (hetero)arylations using and heteroaryl halides enabled by a chiral cobalt-bisphosphine catalyst. This approach shows good functional group compatibility complements reported strategy without use reagents. Mechanistic investigations supported that aryl-cobalt, instead an arylzinc reagent, was formed in situ this aryl-addition event.

Язык: Английский

Процитировано

23

Photoredox/Nickel Dual Catalysis-Enabled Modular Synthesis of Arylallyl Alcohols with Acetylene as the Two-Carbon Synthon DOI

Kangkui Li,

Xianyang Long,

Shifa Zhu

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(4), С. 2422 - 2431

Опубликована: Фев. 2, 2023

Arylallyl alcohols are commonly found in natural products and drug molecules. The traditional syntheses primarily rely on two-component reactions using presynthesized alkenes. Herein, we report a photoredox/nickel dual-catalyzed three-component cross-coupling reaction, which enables the rapid synthesis of arylallyl with acetylene as two-carbon (C2) synthon. In this aryl halide carbonyl compound were sewn together linker. A series synthesized an atmosphere (1 atm). This method features broad substrate scopes, good functional group tolerance, high Z-selectivity. addition to intermolecular difunctionalization acetylene, reaction is also amenable intramolecular ring formation, giving highly valuable indenols indanones. mechanistic investigation indicates that alkenylnickel key intermediate. intermediate can be considered alternative alkenyl Grignard reagent but better compatibility. With step, several important molecules including have been prepared.

Язык: Английский

Процитировано

20

Visible Light‐Mediated Cobalt and Photoredox Dual‐Catalyzed Asymmetric Reductive Coupling for Axially Chiral Secondary Alcohols DOI

Tianlong Liang,

Yingtao Wu,

Jiaqiong Sun

и другие.

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(23), С. 3253 - 3260

Опубликована: Июль 20, 2023

Comprehensive Summary Secondary alcohols bearing both axial and central chirality comprise attractive biological activity exhibit excellent chiral induction in asymmetric reactions. However, only very limited catalytic approaches were developed for their synthesis. We herein describe visible light‐mediated cobalt‐catalyzed reductive Grignard‐type addition of aryl iodides with axially prochiral biaryl dialdehydes leading to the direct construction secondary alcohols. Preliminary mechanistic studies indicate that efficient kinetic recognition diastereomers might occur improve stereoselectivity, which open a new avenue challenging cascade multiple elements. This protocol features enantio‐ diastereoselectivity, green mild conditions, simple operation, broad substrate scope, providing modular platform synthesis

Язык: Английский

Процитировано

20