Rhodium-catalyzed atropodivergent hydroamination of alkynes by leveraging two potential enantiodetermining steps DOI Creative Commons

Ruijie Mi,

Rong-Kai Wu,

Jierui Jing

и другие.

Science Advances, Год журнала: 2024, Номер 10(48)

Опубликована: Ноя. 27, 2024

A pair of enantiomers is known to have different biological activities. Two catalysts with opposite chirality are nearly always required deliver both enantiomeric products. In this work, chiral rhodium(III) cyclopentadienyl complexes repurposed as efficient for enantiodivergent and atroposelective hydroamination sterically hindered alkynes. Products been obtained using the same or closely analogous catalyst in good efficiency excellent enantioselectivity, enantiodivergence was mainly enabled by an achiral carboxylic acid its silver salt. Mechanistic studies revealed origin ascribable switch enantiodetermining step (alkyne insertion versus protonolysis) under control, which constitutes a previously unidentified working mode leveraging two elementary steps.

Язык: Английский

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field DOI
Hong‐Hao Zhang,

Tian‐Zhen Li,

Si‐Jia Liu

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(3)

Опубликована: Ноя. 2, 2023

With the rapid development of asymmetric catalysis, demand for enantioselective synthesis complex and diverse molecules with different chiral elements is increasing. Owing to unique features atropisomerism, catalytic atropisomers has attracted a considerable interest from chemical science community. In particular, introducing additional elements, such as carbon centered chirality, heteroatomic planar helical into provides an opportunity incorporate new properties axially compounds, thus expanding potential applications atropisomers. Thus, it important perform transformations synthesize bearing multiple elements. spite challenges in transformations, recent years, chemists have devised powerful strategies under organocatalysis or metal synthesizing wide range enantioenriched Therefore, become emerging field. This review summarizes progress this field indicates challenges, thereby promoting horizon.

Язык: Английский

Процитировано

74

Pd-catalyzed asymmetric Larock reaction for the atroposelective synthesis of N─N chiral indoles DOI Creative Commons
Jinlei Wang, Deng Pan, Fen Wang

и другие.

Science Advances, Год журнала: 2024, Номер 10(19)

Опубликована: Май 10, 2024

Atropisomeric indoles defined by a N─N axis are an important class of heterocycles in synthetic and medicinal chemistry material sciences. However, they remain heavily underexplored due to limited methods challenging stereocontrol over the short bonds. Here, we report highly atroposelective access axially chiral via asymmetric Larock reaction. This protocol leveraged powerful role phosphoramidite ligand attenuate common dissociation original reaction, forming with excellent functional group tolerance high enantioselectivity palladium-catalyzed intermolecular annulation between readily available o -iodoaniline alkynes. The multifunctionality prepared allowed diverse post-coupling transformations, affording broad array functionalized indoles. Experimental computational studies have been conducted explore reaction mechanism, elucidating enantio-determining rate-limiting steps.

Язык: Английский

Процитировано

8

Construction of axial and point chirality through Ni-catalyzed sila-cycloaddition reaction via desymmetrization and (dynamic) kinetic resolution DOI
Hua‐Jie Zhu, Minghao Shen,

Jia-Wei Si

и другие.

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 6, 2025

Язык: Английский

Процитировано

0

Access to distal biaxial atropisomers by iridium catalyzed asymmetric C–H alkylation DOI Creative Commons
Xueqing Hu,

Yunxu Zhao,

Tong He

и другие.

Chemical Science, Год журнала: 2024, Номер 15(33), С. 13541 - 13549

Опубликована: Янв. 1, 2024

Herein, we report an iridium-catalyzed asymmetric C–H activation combined with a desymmetrization strategy for synthesizing distal biaxial atropisomers excellent stereoselectivity, displaying promising photophysical and chiroptical properties.

Язык: Английский

Процитировано

3

Atroposelective synthesis of N–N axially chiral pyrrolyl(aza)-quinolinone by de novo ring formation DOI
Qiwen Huang, Yanze Li, Cun Yang

и другие.

Organic Chemistry Frontiers, Год журнала: 2023, Номер 11(3), С. 726 - 734

Опубликована: Дек. 4, 2023

A chiral phosphoric acid-catalyzed Paal–Knorr reaction was achieved for constructing axially pyrrolyl(aza)quinolinones with ‘6–5’-membered rings as a new family member of N–N atropisomers.

Язык: Английский

Процитировано

7

Progress in Asymmetric Catalytic Synthesis of C—N Axis Chiral Compounds DOI Open Access
Wanting Chen, Xiongwei Zhong, Jiale Xing

и другие.

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(2), С. 349 - 349

Опубликована: Янв. 1, 2024

Enantioenriched C-N axial chiral compounds are ubiquitous in many important field, such as natural products, drugs and ligands.Therefore, efficient construction of axis chirality through asymmetric catalytic synthesis has attracted more attention research interest.In this review, the recent progress been discussed, mainly from three aspects: desymmetrization prochiral molecules or kinetic resolution racemates, atroposelective functionalization axis, coupling reaction.The topic focuses on evolution system key factors control.The existing problems future development direction field also discussed.This paper is a timely systematic review will stimulate extensive interest.

Язык: Английский

Процитировано

2

Rh(III)-Catalyzed Diastereo- and Enantioselective Regiodivergent (Hetero)Arylamidation of (Homo)Allylic Sulfides DOI
Xiaoyan Jia,

Gui-Lin Hao,

Mengxia Feng

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(14), С. 9768 - 9778

Опубликована: Март 28, 2024

A rhodium-catalyzed 3-component conjunctive diastereo- and regioselective arylamidation of (homo)allylic sulfides, organon boronic acids, dioxazolones is reported. These reactions deliver the 1,2-insertion 2,1-insertion products, respectively, for allylic sulfides homoallylic sulfides. The enantioselective terminal internal achieved, furnishing various 1,3-N,S compounds featuring one or two contiguous stereocenters in high yields with enantioselectivities. Mechanistic studies suggest a change turnover-limiting selectivity-determining steps induced by native easily removable sulfide group.

Язык: Английский

Процитировано

2

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field DOI
Hong‐Hao Zhang,

Tian‐Zhen Li,

Si‐Jia Liu

и другие.

Angewandte Chemie, Год журнала: 2023, Номер 136(3)

Опубликована: Ноя. 2, 2023

Abstract With the rapid development of asymmetric catalysis, demand for enantioselective synthesis complex and diverse molecules with different chiral elements is increasing. Owing to unique features atropisomerism, catalytic atropisomers has attracted a considerable interest from chemical science community. In particular, introducing additional elements, such as carbon centered chirality, heteroatomic planar helical into provides an opportunity incorporate new properties axially compounds, thus expanding potential applications atropisomers. Thus, it important perform transformations synthesize bearing multiple elements. spite challenges in transformations, recent years, chemists have devised powerful strategies under organocatalysis or metal synthesizing wide range enantioenriched Therefore, become emerging field. This review summarizes progress this field indicates challenges, thereby promoting horizon.

Язык: Английский

Процитировано

5

Rhodium-catalyzed atropodivergent hydroamination of alkynes by leveraging two potential enantiodetermining steps DOI Creative Commons

Ruijie Mi,

Rong-Kai Wu,

Jierui Jing

и другие.

Science Advances, Год журнала: 2024, Номер 10(48)

Опубликована: Ноя. 27, 2024

A pair of enantiomers is known to have different biological activities. Two catalysts with opposite chirality are nearly always required deliver both enantiomeric products. In this work, chiral rhodium(III) cyclopentadienyl complexes repurposed as efficient for enantiodivergent and atroposelective hydroamination sterically hindered alkynes. Products been obtained using the same or closely analogous catalyst in good efficiency excellent enantioselectivity, enantiodivergence was mainly enabled by an achiral carboxylic acid its silver salt. Mechanistic studies revealed origin ascribable switch enantiodetermining step (alkyne insertion versus protonolysis) under control, which constitutes a previously unidentified working mode leveraging two elementary steps.

Язык: Английский

Процитировано

0