Strategies and Methods for the Catalytic Asymmetric Synthesis of Benzofuran/Benzopyran Fused Acetals: A Review DOI
Yushuang Chen, Yulong Zhang, Dong Zhang

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4320 - 4333

Published: Nov. 17, 2023

Benzofuran- and benzopyran-fused polycyclic acetals are found in a variety of biologically active natural products. The synthetic methods toward this class heterocycles have fascinated one the most intensive pursuits total synthesis. Nevertheless, stereoselective towards rapid construction such skeletons still remain challenging for organic chemists. Significant progress has been made research area recent years, however, literature on enantioselective approaches to construct these molecules not fully reviewed. Driven by their intriguing complex scaffolds with potential usefulness, we compose advances review covering all important works field. We hope will promote future area.

Language: Английский

Enantioselective Synthesis of Dihydropyrazoles by Palladium/Xu‐Phos‐Catalyzed Alleneamination of β,γ‐Unsaturated Hydrazones with Propargylic Acetates DOI
Shuting Zhang,

Shuaijie Wu,

Qiang Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 10, 2023

The palladium-catalyzed asymmetric carboamination reaction is one of the most significant transformations in organic chemistry. Herein, we report first alleneamination β,γ-unsaturated hydrazones with propargylic acetates. This protocol enables efficient installation various multisubstituted allene groups onto dihydropyrazoles good yields excellent enantioselectivities. chiral sulfinamide phosphine ligand Xu-5 exhibits highly stereoselective control this protocol. salient features include readily available starting materials, a broad substrate scope, an easy scale-up, mild conditions and versatile transformations.

Language: Английский

Citations

20
Anti-selective [3+2] (Hetero)annulation of non-conjugated alkenes via directed nucleopalladation DOI Creative Commons

Hui‐Qi Ni,

Ilia Kevlishvili,

Pranali G. Bedekar

et al.

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: Dec. 22, 2020

2,3-Dihydrobenzofurans and indolines are common substructures in medicines natural products. Herein, we describe a method that enables direct access to these core structures from non-conjugated alkenyl amides ortho-iodoanilines/phenols. Under palladium(II) catalysis this [3 + 2] heteroannulation proceeds an anti-selective fashion tolerates wide variety of functional groups. N-Acetyl, -tosyl, -alkyl substituted ortho-iodoanilines, as well free -NH

Language: Английский

Citations

50
Chiral oxalamide phosphine (COAP)-Pd-catalyzed enantioselective cascade formal [4 + 1] annulation for enantioenriched 2,3-disubstituted indolines and further DFT study on regio- and stereocontrol DOI

Sheng‐Suo Zhou,

Junhao Shen, Wenkai Liu

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(9), P. 2138 - 2146

Published: Jan. 1, 2023

COAP-Pd-catalyzed asymmetric cascade formal [4 + 1] annulation was developed between racemic vinyl benzoxazinones and N -tosylhydrazone sodium salts, affording trans -2,3-disubstituted indolines in good yields with high stereoselectivity.

Language: Английский

Citations

14
Pd-Catalyzed Enantioselective Three-Component Carboamination of 1,3-Cyclohexadiene DOI

Jinrong Wang,

Bing Xu, Yibo Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21231 - 21238

Published: July 29, 2024

Asymmetric Pd-catalyzed three-component carboamination reactions of dienes to construct chiral cyclohexenylamines, which are great importance in many fields chemistry, have remained largely unexplored. Here, we demonstrate a highly enantio- and regioselective Pd/Ming-Phos-catalyzed 1,3-cyclohexadiene with readily available aryl iodides anilines for facile access diverse valuable cyclohexenylamines. The process shows excellent functional group tolerance, easy scalability, mild conditions. Moreover, mechanistic studies suggest that this reaction has first-order dependence on the concentration palladium catalyst aniline.

Language: Английский

Citations

6
Recent advances in palladium-catalyzed (hetero)annulation of CC bonds with ambiphilic organo(pseudo)halides DOI

Hui‐Qi Ni,

Phillippa Cooper, Keary M. Engle

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(62), P. 7610 - 7624

Published: Jan. 1, 2021

Palladium has proven to be effective in catalyzing the (hetero)annulation of C[double bond, length as m-dash]C bonds with ambiphilic organo(pseudo)halides. Through employment appropriate coupling partners, efficient annulation a variety allenes, 1,3-dienes, strained alkenes, styrenes, and other bond variants can achieved provide direct access numerous useful hetero- carbocyclic scaffolds. In this Feature Article, we summarize palladium-catalyzed methods reported since 2005 (spanning just over 15 years) discuss outstanding challenges area study.

Language: Английский

Citations

29
Ligand-dependent, palladium-catalyzed stereodivergent synthesis of chiral tetrahydroquinolines DOI Creative Commons
Yue Wang, Er‐Qing Li, Zheng Duan

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(27), P. 8131 - 8136

Published: Jan. 1, 2022

The most fundamental tasks in asymmetric synthesis are the development of fully stereodivergent strategies to access full complement stereoisomers products bearing multiple stereocenters. Although great progress has been made past few decades, developing general and practical that allow selective generation any diastereomer a reaction product stereocentres through switching distinct chiral catalysts is significant challenge. Here, attaining precise stereochemistry, we develop novel

Language: Английский

Citations

21
PC-Phos Enabled Catalytic Palladium-heteroallyl Asymmetric Cycloaddition DOI
Wenge Zhang, Peichao Zhang, Yin-Lin Li

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(42), P. 19627 - 19634

Published: Oct. 18, 2022

Asymmetric cycloaddition reactions are the most powerful tool to expeditious construction of enantioenriched cyclic motifs in organic chemistry. In sharp contrast well-developed via palladium-trimethylenemethane (Pd-TMM) intermediate, hetero (3 + 2) cycloadditions heteroallyl cations remain rare, largely due their thermally forbidden nature. To best our knowledge, there is no example asymmetric version leading heterocycles reported so far. Herein we enabled first catalytic electrophilic palladium-heteroallyl zwitterion intermediate (Pd-OTMM or Pd-NTMM) with acyclic 1,3-dienes a pathway terminated C–N C–O bond formation, delivering highly substituted fused pyrrolidine and tetrahydrofuran rings high yields excellent regio-, diastereo-, enantioselectivity. Engineering PC-Phos, one chiral sulfinamide phosphine (Sadphos) type ligands, by introducing di-tert-butyl or/and 3,5-difluorophenyl group vital component achieving reactivity

Language: Английский

Citations

21
Transition Metal‐Catalyzed Carboamination of Alkenes and Allenes: Recent Progress DOI
Santosh K. Nanda,

Rosy Mallik

Asian Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 11(1)

Published: Oct. 9, 2021

Abstract Vicinal carboamination of carbon‐carbon multiple bonds is a highly reliable and efficient practical strategy for the quick preparation valuable diverse amine derivatives starting from simple synthons. The last decade has witnessed numerous methods employing transition metal approaches alkenes allenes synthesis these N‐bearing entities. Driven by renaissance catalysis, inter‐and intramolecular comprising concomitant C−N C−C bond formation been studied extensively. Interestingly, existing reviews describing developments on are mostly reaction path specific confined to particular catalyst. Whereas, guiding congregation literature allene not documented. In this review, different conceptual will be discussed examples recent presented with special focus detailed mechanism.

Language: Английский

Citations

24
Gold-Catalyzed 1,1-Carboalkoxylation of Oxetane-Ynamides via Exocyclic Metal Carbenes: Divergent and Atom-Economical Synthesis of Tricyclic N-Heterocycles DOI
Linjun Qi,

Chong‐Yang Shi,

Pengfei Chen

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(6), P. 3679 - 3686

Published: March 9, 2021

Transition-metal-catalyzed intramolecular carboalkoxylation of alkynes has attracted much attention in the past decades due to its high bond-forming efficiency and atom economy rapid assembly functionalized cyclic compounds. However, compared with well-established alkyne 1,2-carboalkoxylation, related 1,1-carboalkoxylation been far less exploited. Here, we report an unprecedented gold-catalyzed ynamides for generation exocyclic gold carbenes via exo-cyclization under room temperature. Subsequent 1,2-N-migration 1,2-H-migration into lead divergent atom-economical synthesis valuable tetrahydrofuran-fused 1,4-dihydroquinolines furoindolines. Moreover, asymmetric these tricyclic N-heterocycles can be achieved by a chirality-transfer strategy, possibility enantioselective cyclization chiral kinetic resolution also emerges. In addition, mechanistic rationale this 1,1-carboalkoxylation, particular accounting distinct migration carbenes, is strongly supported theoretical calculations.

Language: Английский

Citations

21
Synthesis of W‐Phos Ligand and Its Application in the Copper‐Catalyzed Enantioselective Addition of Linear Grignard Reagents to Ketones DOI
Wenjun Luo, Liming Zhang, Zhan‐Ming Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(29)

Published: May 12, 2022

The asymmetric catalytic addition of linear Grignard reagents to ketones has been a long-standing challenge in organic synthesis. Herein, novel family PNP ligands (W-Phos) was designed and applied copper-catalyzed aryl alkyl ketones, allowing facile access versatile chiral tertiary alcohols good high yields with excellent enantioselectivities (up 94 % yield, 96 ee). process can also be used synthesize allylic from more challenging α,β-unsaturated ketones. Notably, the potential utility this method is demonstrated gram-scale synthesis modification various densely functionalized medicinally relevant molecules.

Language: Английский

Citations

16