Pd/Cu-Cocatalyzed Asymmetric Cascade Heck/Tsuji–Trost Reaction to Access Non-natural Tryptophans DOI
Panpan Li, Yang Zhang,

Zijiao Liu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 20, 2024

A Pd-catalyzed asymmetric Heck cascade reaction involving the intramolecular carbopalladation of unsaturated hydrocarbons, followed by nucleophilic trapping resulting palladium species, is a powerful approach for constructing chiral N-heterocycles. However, use prochiral nucleophiles in these reactions remains significantly underexplored. Herein, we report novel Pd/Cu catalytic system Heck/Tsuji–Trost allenamides and aldimine esters. This robust method allows rapid synthesis wide range enantiopure non-natural α-substituted tryptophans high yields (up to 99% yield) with excellent enantioselectivities 98% ee). Additionally, synthetic utility this protocol demonstrated through scale-up experiments diverse valuable transformations.

Language: Английский

Interrupting Associative π–σ–π Isomerization Enables Z-Retentive Asymmetric Tsuji–Trost Reaction DOI
Jiandong Liu,

Z. X. Dong,

Wenbin Cao

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(3), P. 2776 - 2785

Published: Jan. 8, 2025

The asymmetric Tsuji-Trost reaction has been extensively studied due to its importance in establishing stereogenic centers, often adjacent an E-olefin moiety organic molecules. generally preferential formation of chiral products is believed result from the thermodynamically more stable syn-π-allylpalladium intermediate. rapid associative π-σ-π isomerization makes it challenging synthesize Z-olefin via transient anti-π-allylpalladium Herein, we report a strategy for regulating by tuning steric bulkiness ligands, allylic leaving groups, and counteranions. utilization Pd catalyst derived phosphoramidite ligands interrupts isomerization, enabling highly efficient Z-retentive toward array α-amino acid derivatives bearing motif high yields (up 95%) excellent stereoselectivity 99% ee >19:1 Z/E) with low loading (0.1 mol %). mechanistic insights design reported this work pave way rational developments Tsuji-Trost-type reactions.

Language: Английский

Citations

3
Asymmetric Allylic Substitution Reactions Based on Relay Catalysis DOI
Xiaoming Feng, Yangbin Liu, Zhenwei Wu

et al.

Synthesis, Journal Year: 2024, Volume and Issue: 56(22), P. 3349 - 3364

Published: March 5, 2024

Abstract Transition-metal-catalyzed asymmetric allylic substitution reactions represent a hot research topic in the field of synthesis, with significant progress having been made. Among diverse catalysis systems, relay enables sequential activation multiple steps one pot and rapid construction chiral centers, providing simple powerful platform for organic synthesis. Recently, has successfully applied to reactions, variety challenging transformations have realized. This Short Review summarizes related on based over last decade. 1 Introduction 2 The General Transformation Model 3 Allylation Relays Further Reaction 4 Initial 5 Conclusion Outlook

Language: Английский

Citations

4
Pd-Catalyzed Three-Component Coupling of Cyclopropenones via Sequential C–C Bond Activation and Allylation DOI
Zhou Zhang,

Feifei Liang,

Shulin Zhang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4262 - 4267

Published: May 9, 2024

A novel Pd-catalyzed three-component domino reaction for the stereoselective synthesis of highly functionalized allyl cinnamates has been developed. In this protocol, a sequential process C–C bond activation and intermolecular allylic substitution was well-organized. The key transformation is in situ generated hydrolysis product cyclopropenone, which triggered new with vinylethylene carbonates. mechanism investigated, demonstrating high stereoselectivity excellent atomic economy process.

Language: Английский

Citations

4
Tandem catalytic allylic C–H amination and asymmetric [2,3]-rearrangement via bimetallic relay catalysis DOI Creative Commons
Zhenwei Wu, Xi Yang, Fangqing Zhang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(33), P. 13299 - 13305

Published: Jan. 1, 2024

An asymmetric tandem allylic C–H amination and [2,3]-sigmatropic rearrangement has been developed by making use of bimetallic relay catalysis with an achiral Pd(0) catalyst a chiral N,N ′-dioxide-Mg( ii ) complex.

Language: Английский

Citations

4
Pd/Cu-Cocatalyzed Enantio- and Diastereodivergent Wacker-Type Dicarbofunctionalization of Unactivated Alkenes DOI

Wenzhi Zhu,

Chongyu Han,

Guoqiang Yang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(38), P. 26121 - 26130

Published: Aug. 5, 2024

The Wacker and Wacker-type reactions are some of the most fundamental powerful transformations in organic chemistry for their ability to efficiently produce valuable chemicals. Remarkable progress has been achieved asymmetric oxy/aza-Wacker-type reactions; however, dicarbofunctionalization remains underdeveloped, especially concurrent construction two stereocenters. Herein, we report a Pd/Cu-cocatalyzed enantio- diastereodivergent alkene-tethered aryl triflates with imino esters. A series 2-indanyl motifs bearing adjacent carbon stereocenters could be easily synthesized moderate excellent yields good diastereo- enantioselectivities (up >20:1 dr >99% ee). Density functional theory calculations revealed that origin diastereoselectivity this Pd/Cu synergistic catalytic system is jointly determined by both intermolecular anti-carbopalladation alkenes reductive elimination processes, accordance Curtin–Hammett principle.

Language: Английский

Citations

4
Cu-catalyzed enantioselective assembly of axially chiral allylic boronates DOI
Shuai Wang, Jianbo Liu,

Wenyue Ma

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 25, 2024

Language: Английский

Citations

4
Cooperative Pd/Chiral Secondary Amine Enabled Diastereo- and Enantioselective [3 + 2] Cycloannulation: Synthesis of Polysubstituted Cyclopentanes DOI
Zhiyong Luo, Limei Gao, Dongqing He

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

A cooperative palladium/chiral amine enabled diastereo- and enantioselective [3 + 2] cycloaddition of π-allyl 1,3-dipoles with α,β-unsaturated aldehydes has been developed. series highly functionalized cyclopentanes bearing three continuous tertiary stereocenters can be facilely efficiently obtained in good to excellent yields (51-97%) synthetically useful enantioselectivity (93-99% ee) under mild reaction conditions. Control experiments HRMS analyses were conducted elucidate the possible mechanism. The utility current method was demonstrated by gram-scale synthesis elaboration products into various cyclopentanes.

Language: Английский

Citations

0
Catalyst-controlled regiodivergence and stereodivergence in formal cross-[4+2] cycloadditions: The unique effect of bismuth(III) DOI
Qiumeng Hou,

Chenxi Cai,

Shuai‐Jiang Liu

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(13)

Published: March 26, 2025

The [4+2] cycloaddition is crucial for constructing six-membered rings in pharmaceuticals and natural products. Cross-[4+2] cycloadditions offer greater product diversity than traditional diene-dienophile reactions due to multiple possible pathways. However, precise control over regio- stereoselectivity various isomers remains a great challenge. This study reports catalyst-controlled regiodivergent formal cross-cycloadditions of acyclic dienes enones, significantly enhancing access diverse pyrazole-fused spirooxindoles. Chiral phosphoric acid (CPA) catalysis enables endoselective cycloadditions, while Bi(III) with CPA ligand yields [2+4] products high stereoselectivity. A Claisen rearrangement the adduct produces exo-selective product, further increasing stereochemical enabling synthesis six stereo-isomers from single substrate set. DFT calculations reveal that reverses regioselectivity by repositioning reactants pocket stabilizing enone oxygen’s negative charge. In addition, 3as demonstrates therapeutic potential against triple-negative breast cancer, an IC 50 8.5 μM MDA-MB-453 cells.

Language: Английский

Citations

0
Sulfonated Phosphine‐Palladium/Bisguanidinium Ion Pair Catalyzed Enantioselective Allylic Amination DOI

Long‐Yi Xi,

R. Panner Selvam,

Chen Xu

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 24, 2025

Comprehensive Summary In this study, we successfully developed ion pair catalysts consisting of chiral bisguanidinium (BG) cations and non‐chiral sulphonated phosphine‐palladium complexes as counterions. These pairs catalyzed allylic alkylation reactions with excellent enantioselectivities. Furthermore, these can be easily performed on a gram‐scale, demonstrating their potential for industrial applications. We were able to obtain 1 H NMR the catalyst identified 31 P complex.

Language: Английский

Citations

0
Pd-Catalyzed Three-Component 1,1-Carboamination of 4-Pentenoic Acid DOI

Lihua Mao,

Xiangwen Tan,

Jiahao Wu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 13, 2025

Herein, we describe a method to achieve the three-component 1,1-carboamination of 4-pentenoic acid by palladium catalysis, successfully constructing δ-lactam derivatives. The protocol features excellent 1,1-regioselectivity, high step and atom economy, good functional group tolerance.

Language: Английский

Citations

0