Torsional Strain‐Independent Catalytic Enantioselective Synthesis of Biaryl Atropisomers DOI

Zhang‐Hong Luo,

Wentao Wang,

Tian‐Yi Tang

et al.

Angewandte Chemie, Journal Year: 2022, Volume and Issue: 134(43)

Published: Aug. 26, 2022

Abstract Catalytic asymmetric dynamic kinetic resolution of configurationally labile bridged biaryls is emerging as a powerful strategy for atropisomer synthesis. However, the reported examples suffer from an inherent challenge reactivity highly dependent on torsional strain biaryl substrates, which significantly narrows down scope and hampers application. Herein, we report our discovery development strain‐independent reaction between thionolactones activated isocyanides. By employing auto‐tandem silver catalysis, universal synthesis both tri ‐ tetra ortho ‐substituted thiazole‐containing was realized in high yields with enantioselectivities. In addition, these products could be facilely converted to novel type bearing eight‐membered lactone. Mechanistic studies were carried out elucidate cause this unusual reactivity.

Language: Английский

Transition Metal-Catalyzed Biaryl Atropisomer Synthesis via a Torsional Strain Promoted Ring-Opening Reaction DOI
Xue Zhang, Kun Zhao, Zhenhua Gu

et al.

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(12), P. 1620 - 1633

Published: June 1, 2022

ConspectusArising from the restricted rotation of a single bond caused by steric or electronic effects, atropisomerism is one few fundamental categories for molecules to manifest their three-dimensional characters into which axially chiral biaryl compounds fall. Despite widespread occurrence skeletons in natural products, bioactive molecules, and ligands/organocatalysts, catalytic asymmetric methods synthesis these structures still lag behind demand. Major challenges preparation biaryls include accessing highly sterically hindered variants while controlling stereoselectivity. A couple useful strategies have emerged direct last two decades.Recently, we engaged atropisomers via transition metal catalysis, including ring-openings dibenzo cyclic compounds. During studies, serendipitously discovered that substituents adjacent axis cause be distorted minimize repulsion. The display higher reactivity ring-opening reactions than non-distorted molecules. In other words, torsional strain can promote reaction. On basis this concept, successfully realized reaction diaryliodoniums, silanes, 9H-fluoren-9-ols, delivered several differently substituted ortho tetra-substituted high enantioselectivity. not only activates substrates toward under mild conditions but also changes chemoselectivity bond-breaking events. palladium-catalyzed carboxylation S-aryl dibenzothiophenium, inversed selectivity exocyclic C–S cleavage reaction.In Account, summarize our studies on copper-, rhodium-, as collection straightforward with enantiopurity above-mentioned strain-promoted coupling strategy. part, energies are discussed aid density functional theory (DFT) calculations.

Language: Английский

Citations

129
Atroposelective catalysis DOI

Tanno A. Schmidt,

Valeriia Hutskalova,

Christof Sparr

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

Citations

21
Developing Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki–Miyaura Cross-Coupling DOI

Yiming Yang,

Changhui Wu,

Junhao Xing

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6283 - 6293

Published: Feb. 21, 2024

We herein introduce biarylhemiboronic esters as a new type of bridged biaryl reagent for asymmetric synthesis axially chiral structures, and the palladium-catalyzed Suzuki-Miyaura cross-coupling is developed. This dynamic kinetic atroposelective coupling reaction exhibits high enantioselectivity, good functional group tolerance, broad substrate scope. The synthetic application current method was demonstrated by transformations product programmed polyarene. Preliminary mechanistic studies suggested that proceeded via an enantio-determining transmetalation step.

Language: Английский

Citations

18
Palladium‐Catalyzed Stereoselective Cleavage of C−P Bond: Enantioselective Construction of Atropisomers Containing a P‐Stereogenic Center DOI Open Access

Liangzhi Pang,

Qilin Sun,

Zhan Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(47)

Published: Sept. 28, 2022

The transition-metal-catalyzed C-P bond cleavage has emerged as a powerful tool for the formation of both C-C and bond. However, stereoselective is still undeveloped. Herein, we report palladium-catalyzed construction P-stereogenic phosphines stereogenic axis. This protocol enables quick synthesis atropisomers bearing center in high yields, diastereo- enantioselectivities up to 98 % ee, >25 : 1 dr. product able serve chiral catalyst phosphine catalyzed [3+2] cycloaddition allenoates imines, showing great potential present methodology.

Language: Английский

Citations

41
Palladium-catalyzed regio- and stereo-selective phosphination of cyclic biarylsulfonium salts to access atropoisomeric phosphines DOI Creative Commons

Jinghui Sun,

Yifei Yan,

Xuanxuan Chen

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(18), P. 6943 - 6948

Published: Jan. 1, 2024

A Pd-catalyzed atroposelective phosphination of cyclic biarylsulfonium salts with HPAr 3 Ar 4 for straightforward synthesis chiral phosphines bearing a stereogenic axis or both and P-stereogenic center is reported.

Language: Английский

Citations

9
Catalytically atroposelective ring-opening of configurationally labile compounds to access axially chiral biaryls DOI
Guanjie Wang, Jie Huang, Junmin Zhang

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(16), P. 4507 - 4521

Published: Jan. 1, 2022

In this minireview, we evaluate and summarize the construction of axially chiral biaryls, briefly state our personal perspectives on future advancement direction.

Language: Английский

Citations

27
Palladacycle-Catalyzed Olefinic C–P Cross-Coupling of Alkenylsulfonium Salts with Diarylphosphines to Access Alkenylphosphines DOI
Jie Zhu, Yun Ye, Yinhua Huang

et al.

Organometallics, Journal Year: 2022, Volume and Issue: 41(16), P. 2342 - 2348

Published: Aug. 4, 2022

An efficient olefinic C–P cross-coupling of alkenylsulfonium salts with secondary diarylphosphines is reported. The use a palladacycle enables the facile formation bond at alkenyl moiety tolerating wide range functional groups under mild conditions. This protocol provides an easy access to various alkenylphosphine products in good high yields levels stereoselectivity (E selectivity).

Language: Английский

Citations

24
Chiral Phosphoric Acid Catalyzed Asymmetric Hydrolysis of Biaryl Oxazepines for the Synthesis of Axially Chiral Biaryl Amino Phenol Derivatives DOI

Liwen Wei,

Jiaomeng Li, Yi Zhao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(39)

Published: June 20, 2023

The development of catalytic asymmetric reaction with water as the reactant is challenging due to reactivity- and stereoselectivity-control issues resulted from low nucleophilicity small size water. We disclose herein a chiral phosphoric acid (CPA) catalyzed atroposelective ring-opening biaryl oxazepines A series undergo CPA hydrolysis in highly enantioselective manner. key for success this use new SPINOL-derived catalyst high reactivity oxazepine substrates towards under acidic conditions. Density functional theory calculations suggest that proceeds via dynamic kinetic resolution pathway addition imine group both enantio- rate-determining.

Language: Английский

Citations

15
Development of Configurationally Labile Biaryl Reagents for Atropisomer Synthesis DOI
Changhui Wu, Jin Yang, Xiaoyuan Zhang

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(28)

Published: May 16, 2024

Abstract Axially chiral biaryl scaffolds are important in pharmaceuticals, natural products, and asymmetric synthesis. Atroposelective ring‐opening of configurationally labile reagents via dynamic kinetic transformation provides a valuable approach to access axially atropisomers. This review summarizes seminal contributions recent advancements on this topic based the use different types reagents.

Language: Английский

Citations

6
Synthesis of Chiral Polycyclic Indoles via Pd(II)-Catalyzed Sequential Cyclization and Carbonylation DOI
Long Chen,

Hengrui Zhou,

Yiji Xue

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8739 - 8747

Published: May 21, 2024

Asymmetric tandem Heck and carbonylation reactions provide an efficient route to synthesize biologically important chiral cyclic compounds with a carbonyl group have attracted increasing research interests. However, this type of reaction relies on the initiation from oxidative addition aryl halides or pseudo halides, resulting in low atomic economy reaction. In addition, protocol has not adequately demonstrated reactivity generality heteroarene halides. Meanwhile, asymmetric Wacker-type cyclization are plagued by narrow substrate scope enantioselectivity remain underexplored. Herein, we describe Pd(II)-catalyzed sequential 1,6-enynes analogues carbon monoxide (CO). This catalytic system tolerates broad nucleophiles, including phenols, alcohols, amines. sequence forms four chemical bonds, two rings, up three stereocenters single step. strategy allows for convenient access variety polycyclic good yields enantio- diastereoselectivities, indoles, benzofurans, indole- benzofuran-fused bicyclo[3.2.1]octanes, indole-fused bicyclo[4.2.1]nonane.

Language: Английский

Citations

6