Enantioselective Vinylogous Addition of Enones to Allenes Enabled by Synergistic Borane/Palladium Catalysis DOI
Heng Luo, Ming Zhang,

Zequn Xing

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 24, 2024

Herein, we report a method for enantioselective vinylogous addition of enones to alkoxyallenes enabled by synergistic borane/palladium catalysis. The inductive effect provided borane coordination the ketone was essential closing gap between conditions needed generation dienolate and those initiation palladium catalytic cycle protonation metal catalyst. Furthermore, accomplished first example stereodivergent synthesis with chiral borane/transition-metal catalysts.

Language: Английский

Stereodivergent Construction of 3,3′-Disubstituted Oxindoles via One-Pot Sequential Allylation/Alkylation and Its Application to the Total Synthesis of Trigolute B and D DOI

Bin Qing,

Zhuang Yang, Zhenwei Wu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

The absolute and relative configurations of bioactive chiral molecules are typically relevant to their biological properties. It is thus highly important desirable construct all possible stereoisomers a lead candidate or given natural compound. Synergistic dual catalysis has been recognized as reliable synthetic strategy for variety predictable stereodivergent transformations. Despite the impressive progress made in this field, carbon-carbon bond-formation reactions involving stabilized nucleophiles remain elusive. Herein, we report an iridium- magnesium-catalyzed one-pot sequential allylic alkylation/nucleophilic alkylation cascade process synthesis four 3,3'-disubstituted oxindoles through three-component reaction. A diverse array products readily prepared with high functional group compatibility good yields excellent diastereo- enantioselectivities. Subsequently, total spirooxindole alkaloid trigolutes B D accomplished concise unified route using same set starting materials.

Language: Английский

Citations

2
Chalcogen Modification: One-Step Strategy for Tuning the Photophysical Properties and NIR Phototherapy of Iodinated BODIPY DOI
Hongyi Liu, Huijun Li, Wen Li

et al.

Materials Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 8(20), P. 3308 - 3320

Published: Jan. 1, 2024

A schematic illustration of iodinated BODIPY based on chalcogen modification the photophysical properties for near-infrared phototherapy tumors.

Language: Английский

Citations

8
Copper-Catalyzed Remote Asymmetric Yne-Allylic Substitution of Yne-Allylic Esters with Anthrones DOI
Tao‐Yan Lin, Meng‐Die Li, Rui Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5758 - 5763

Published: July 1, 2024

Anthrones are key structural motifs in many natural products and pharmaceutical chemicals. However, due to its unique tricyclic aromatic structure, the synthetic space for development of chiral anthrone derivatives is largely limited. By utilizing potential copper-catalyzed remote asymmetric yne-allylic substitution reaction, we describe first example highly regio- enantioselective on various esters with anthrones under a mild reaction condition, which afforded range enantioenriched 1,3-enynes exhibiting broad functional group tolerance across 51 examples.

Language: Английский

Citations

7
Palladium-Catalyzed Enantioselective Intramolecular Heck Reaction to Access Chiral C3-Tertiary Indolines DOI
Tao Liu, Tuanli Yao, Ran Fang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7191 - 7200

Published: April 17, 2025

Language: Английский

Citations

0
Stereodivergent Ruthenium/Copper Relay Catalysis for Modular Access to δ-Lactones with Two Nonadjacent Carbon Stereocenters DOI

G D Song,

Ruiyan Sun, Xia Liu

et al.

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

Published: May 6, 2025

The stereodivergent synthesis of δ-lactones, which are prevalent in natural product frameworks, from simple starting materials via a single transformation remains significant challenge. Herein, we report an enantio- and diastereodivergent cascade reaction for the modular chiral δ-lactones bearing two nonadjacent quaternary tertiary carbon stereocenters. This approach employs bimetallic Ru/Cu relay catalysis between allylic alcohols azaaryl acetates. method integrates Ru-catalyzed asymmetric borrowing hydrogen reaction, Cu-catalyzed Michael addition, rapid lactonization into one-pot process, with all catalysts substrates introduced at outset. By orthogonal permutation metal catalysts, precise control over relative absolute configurations newly formed stereocenters is achieved, allowing selective access to stereoisomers δ-lactone products predictable efficient manner.

Language: Английский

Citations

0
Ni/Cu Dual‐Catalyzed Propargylation for the Stereodivergent Synthesis of Methohexital DOI Creative Commons
Xihao Chang, Jiayin Zhang, Xiang Cheng

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: July 25, 2024

The development of efficient methodologies for the controlled manufacture specific stereoisomers bearing quaternary stereocenters has prompted advances in a variety scientific disciplines including pharmaceutical chemistry, materials science, and chemical biology. However, complete control absolute relative stereochemical configurations alkyne derivatives remains an unmet synthetic challenge. Herein, Ni/Cu dual-catalyzed asymmetric propargylic substitution reaction is presented to produce propargylated products with all-carbon high yields significant diastereo- enantioselectivities (up >20:1 dr, >99% ee). synthesis all variants methohexital, widely used sedative-hypnotic drug, exemplifies efficacy stereodivergent propargylation.

Language: Английский

Citations

2
Diarenofuran[b]-fused BODIPYs: One-Pot SNAr-Suzuki Synthesis and Properties DOI

Limin He,

Na Li, Yanqing Li

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 15, 2024

We present a streamlined methodology that integrates regioselective tetrahalogen-BODIPY and

Language: Английский

Citations

2
Multifunctionalization of Alkenyl Alcohols via a Sequential Relay Process DOI
Chong Liu, Ling Wang, Haibo Ge

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 30733 - 30740

Published: Oct. 29, 2024

Aryl-substituted aliphatic amines are widely recognized as immensely valuable molecules. Consequently, the development of practical strategies for construction these molecules becomes increasingly urgent and critical. Here, we have successfully achieved multifunctionalization reactions alkenyl alcohols in a sequential relay process, which enables transformation patterns arylamination, deuterated methylenated arylamination to easy access multifarious arylalkylamines. Notably, novel functionalization mode carbonyl groups has been developed facilitate processes deuterium incorporation methylene introduction, thereby providing new means diverse transformations groups. This methodology displays wide tolerance toward functional groups, while also exhibiting good applicability across various skeletal structures alkenols amines.

Language: Английский

Citations

0
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

Citations

0
One-Step Construction of Atropisomers Bearing 1,5-Central and Axial Chirality via Catalytic Diastereo- and Atroposelective Remote Desymmetrizing Alkynylation DOI
Shan Wang, Long Li, Ming Jiang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 18872 - 18883

Published: Dec. 11, 2024

Catalytic asymmetric construction of atropisomers with multiple stereogenic elements has recently become an emerging area. However, general methods that produced bearing remote 1,5-axial and central chirality efficiently stereoselectively are scarce yet highly challenging. We herein report a catalytic diastereo- atroposelective desymmetrizing alkynylation axially prochiral dialkynes ortho-quinone methides (o-QMs), furnishing 1,5-remote centrally elements. The control axis far from the reaction site could be simultaneously achieved during stereoselective C(sp3)–C(sp) bond-forming process to generate center. In addition, kinetic resolution racemic alkynes via o-QMs been developed, further enriching structural diversity 1,5-central axial chirality. present method expands chemical space atropisomeric molecules chiral by facile downstream diversification C–C triple bonds. Finally, can also applied for motifs 1,9- 1,10-stereogenic centers.

Language: Английский

Citations

0