Atroposelective Construction of Tetrasubstituted Axially Chiral Alkene Frameworks DOI
Ying He, Jiayu Zou,

Wan-Yi Xu

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 56(12), P. 1862 - 1872

Published: Dec. 14, 2023

Abstract The construction of axially chiral alkene frameworks is currently one hottest topics in the field organic synthetic chemistry. Compared to traditional molecules, such as biaryls, heterobiaryls, and anilides, synthesis alkenes far more challenging, especially for acyclic tetrasubstituted analogues. In this review, we summarized development strategies analogues, including asymmetric difunctionalization, C–H functionalization, cross-coupling, (dynamic) kinetic resolution, allylic substitution-isomerization. 1 Introduction 2 Synthesis Cyclic Tetrasubstituted Axially Chiral Alkenes 3 Acyclic 4 Summary Outlook

Language: Английский

Catalytic Asymmetric Synthesis of Atropisomers Featuring an Aza Axis DOI
Jia Feng, Chuan‐Jun Lu, Renrong Liu

et al.

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(18), P. 2537 - 2554

Published: Sept. 11, 2023

ConspectusAtropisomers bearing a rotation-restricted axis are common structural units in natural products, chiral ligands, and drugs; thus, the prevalence of asymmetric synthesis has increased recent decades. Research into atropisomers featuring an N-containing (N-X atropisomers) remains its infancy compared with well-developed C-C atropisomer analogue. Notably, N-X could offer divergent scaffolds, which extremely important bioactive molecules. The is recognized as both appealing challenging. Recently, we devoted our efforts to catalytic atropisomers, benzimidazole-aryl N-C indole-aryl hydrogen-bond-assisted pyrrole-pyrrole N-N pyrrole-indole indole-indole atropisomers. To obtain Buchwald-Hartwig reaction amidines or enamines was employed. Using Pd(OAc)2/(S)-BINAP Pd(OAc)2/(S)-Xyl-BINAP catalyst system, were readily obtained. address issue reduced stability diarylamine axis, six-membered intramolecular N-H-O hydrogen bond introduced scaffold. A tandem N-arylation/oxidation process used for phosphoric acid (CPA)-catalyzed N-aryl quinone For copper-mediated Friedel-Crafts alkylation/arylation developed. desymmetrization completed successfully via Cu(OTf)2/chiral bisoxazoline (CuOTf)·Tol/bis(phosphine) dioxide thereby achieving first N/N bipyrrole Asymmetric amination utilized provide bisindole excellent stereogenic control. This scaffold using de novo indole construction strategy. heterobiaryl substantially facilitated palladium-catalyzed transient directing group (TDG)-mediated C-H functionalization. Atropisomeric alkenylation, allylation, alkynylation accomplished Pd(OAc)2/l-tert-leucine system. Herein, summarize work on palladium-, copper-, CPA-catalyzed syntheses Furthermore, application molecule analogues axially ligands demonstrated. Subsequently, briefly discussed terms single crystals obtained rotational barriers. Finally, outlook provided.

Language: Английский

Citations

59
Cobalt-catalyzed atroposelective C−H activation/annulation to access N−N axially chiral frameworks DOI Creative Commons
Tong Li, Linlin Shi,

Xinhai Wang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Aug. 29, 2023

The N-N atropisomer, as an important and intriguing chiral system, was widely present in natural products, pharmaceutical lead compounds, advanced material skeletons. anisotropic structural characteristics caused by its special axial rotation have always been one of the challenges that chemists strive to overcome. Herein, we report efficient method for enantioselective synthesis axially frameworks via a cobalt-catalyzed atroposelective C-H activation/annulation process. reaction proceeds under mild conditions using Co(OAc)2·4H2O catalyst with salicyl-oxazoline (Salox) ligand O2 oxidant, affording variety products high yields enantioselectivities. This protocol provides approach facile construction atropisomers further expands range derivatives. Additionally, electrocatalysis, desired were also successfully achieved good excellent efficiencies

Language: Английский

Citations

53
Pd-Catalyzed Asymmetric Larock Indole Synthesis to Access Axially Chiral N-Arylindoles DOI
Genwei Zhang, Bin Yang, Junfeng Yang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5493 - 5501

Published: Feb. 13, 2024

Larock indole synthesis is one of the most straightforward and efficient methods for indoles; however, there has been no asymmetric version yet construction indole-based axially chiral N-arylindoles since its initial report in 1991. Herein we first example an by employing a sulfinamide phosphine (SadPhos) ligand (Ming-Phos) with palladium. It allows rapid wide range N-arylindole compounds good yields up to 98:2 er. The application this unique scaffold as organocatalyst promising. Furthermore, kinetic study revealed that alkyne migratory insertion rate-determining step, which proven density functional theory (DFT) calculations. Additionally, DFT studies also suggest N–C dihedral difference caused steric hindrance contributes enantioselectivity control.

Language: Английский

Citations

23
Cost-effective and high-performance biguanide-incorporated ionic porous organic polymer for selective recovery of Pd(II) and Pt(IV) from metallurgical wastewater DOI

Jiaxing Xiong,

Yuan Zhang, Yan-Jun Chen

et al.

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 488, P. 150772 - 150772

Published: March 28, 2024

Language: Английский

Citations

19
Catalytic asymmetric C–N cross-coupling towards boron-stereogenic 3-amino-BODIPYs DOI Creative Commons
Baoquan Zhan, Li‐Qing Ren,

Jiayi Zhao

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 7, 2025

3-Amino boron dipyrromethenes (BODIPYs) are a versatile class of fluorophores widely utilized in live cell imaging, photodynamic therapy, and fluorescent materials science. Despite the growing demand for optically active BODIPYs, synthesis chiral 3-amino-BODIPYs, particularly catalytic asymmetric version, remains challenge. Herein, we report boron-stereogenic 3-amino-BODIPYs via palladium-catalyzed desymmetric C–N cross-coupling prochiral 3,5-dihalogen-BODIPYs. This approach features broad substrate scope, excellent functional group tolerance, high efficiency, remarkable enantioselectivities, under mild reaction conditions. Further stereospecific formation 3,5-diamino-BODIPYs, along with an investigation into photophysical properties resulting optical BODIPYs also explored. protocol not only enriches chemical space chiroptical BODIPY dyes but contributes to realm chemistry. (BODIPYs), which useful science, authors first cross-couplings.

Language: Английский

Citations

7
Recent advances in Pd-catalyzed asymmetric cyclization reactions DOI
Bing Xu,

Quanpu Wang,

Chao Fang

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 883 - 971

Published: Dec. 18, 2023

This review aims to collect advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years, and it is organized into thirteen sections depending on different types of transformations involved.

Language: Английский

Citations

42
Three-component synthesis ofN-naphthyl pyrazolesviaRh(iii)-catalyzed cascade pyrazole annulation and Satoh–Miura benzannulation DOI

Demao Chen,

Liyun Zhou,

Yunyun Liu

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(27), P. 4036 - 4039

Published: Jan. 1, 2023

The synthesis of N-naphthyl pyrazoles has been realized by the direct three-component reactions enaminones, aryl hydrazine hydrochlorides and internal alkynes via Rh(III) catalysis. synthetic employing simple substrates lead to simultaneous construction dual cyclic moieties, including a pyrazole ring phenyl ring, sequential formation two C-N three C-C bonds.

Language: Английский

Citations

34
Transition-metal-catalyzed enantioselective C–N cross-coupling DOI
Jia Feng, Longlong Xi, Chuan‐Jun Lu

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(19), P. 9560 - 9581

Published: Jan. 1, 2024

Chiral amine scaffolds are among the most important building blocks in natural products, drug molecules, and functional materials, which have prompted chemists to focus more on their synthesis. Among accomplishments chiral synthesis, transition-metal-catalyzed enantioselective C-N cross-coupling is considered one of efficient protocols. This approach combines traditional C(sp

Language: Английский

Citations

10
Simultaneous construction of inherent and axial chirality by cobalt-catalyzed enantioselective C-H activation of calix[4]arenes DOI Creative Commons
Tong Li, Yanbo Zhang, Cong Du

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Sept. 3, 2024

Language: Английский

Citations

10
Pd-Catalyzed Asymmetric Amination of Enamines: Expedient Synthesis of Structurally Diverse N–C Atropisomers DOI Open Access

Peng Zhang,

Chang‐Qiu Guo,

Yao Wang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7680 - 7690

Published: May 23, 2023

The transition-metal-catalyzed cross-coupling of enamines is an attractive method for producing compounds with N–C chiral axis; however, it faces considerable challenges that remain unresolved. Herein, a palladium-catalyzed amination was developed to construct structurally diverse five–six biaryl and six–six nonbiaryl atropisomers. reaction mechanism explained using density functional theory calculations, which showed the involved Curtin–Hammett control. rotation occurred along coordinate until enantio-determining three-centered reductive elimination transition structure established stereochemistry. highly because its broad substrate scope, high stereoselectivity, simple catalytic system, good group tolerance, dynamic kinetic resolution.

Language: Английский

Citations

21