Enantioselective Synthesis of Ten-Membered Lactones via Palladium-Catalyzed [5 + 5] Annulation DOI

Liu Shi,

Qiang Xiong, Shuyi Wu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(12), P. 2030 - 2035

Published: March 20, 2023

Ten-membered lactones are the core units of many biologically active natural products but with a great synthetic challenge. Based on principle vinylogy, novel types cyclic vinylogous anhydrides have been designed as five-carbon carbonyl synthons, further applied in [5 + 5] annulation vinylethylene carbonates under chiral palladium catalysis. This strategy features excellent regioselectivity, mild conditions, and broad substrate scope, affording range spiro ten-membered bearing oxindole pyrrolidinone motif yield (up to 99%) moderate high enantioselectivity 89% ee).

Language: Английский

Advances in Catalytic Asymmetric Reactions Involving o-Hydroxybenzyl Alcohols DOI Open Access
Haiqing Wang, Shuang Yang, Yu‐Chen Zhang

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(3), P. 974 - 974

Published: Jan. 1, 2023

a 江苏师范大学化学与材料科学学院 江苏徐州 221116

Citations

28

Fungicide-inspired precursors of π-allylpalladium intermediates for palladium-catalyzed decarboxylative cycloadditions DOI Creative Commons
Kuan Li,

Shuo Zhen,

Wang Wang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(11), P. 3024 - 3029

Published: Jan. 1, 2023

Inspired by a fungicide, we designed 5-vinyloxazolidine-2,4-diones as new precursors of π-allylpalladium zwitterionic intermediates and developed palladium-catalyzed asymmetric (5 + 3) cycloaddition with azomethine imines (3 2) 1,1-dicyanoalkenes. Both reactions proceeded smoothly under mild reaction conditions to produce various chiral heterocyclic compounds in high yields excellent enantioselectivities. These results revealed that were type suitable precursor for palladium catalysis will find extensive applications Pd-catalyzed such allylic alkylation.

Language: Английский

Citations

27

Recent advances of Pd-π-allyl zwitterions in cycloaddition reactions DOI
Juan Du, Yunfan Li, Chang‐Hua Ding

et al.

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 34(11), P. 108401 - 108401

Published: March 30, 2023

Language: Английский

Citations

25

Recent advances in copper-catalyzed decarboxylative reactions of propargylic cyclic carbonates/carbamates DOI
Yong You, Yanping Zhang, Zhen‐Hua Wang

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(49), P. 7483 - 7505

Published: Jan. 1, 2023

Copper-catalyzed decarboxylative reactions are powerful strategies for the construction of widely available skeletons such as allenes, ethynyl-containing heterocycles, and quaternary carbon centers.

Language: Английский

Citations

23

Palladium-Catalyzed Ligand-Directed Divergent Decarboxylative Cycloadditions of Vinyloxazolidine-2,4-diones with 1,3,5-Triazinanes DOI
Zhen‐Hua Wang, Xiaohui Fu, Qun Li

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1589 - 1594

Published: Feb. 22, 2024

This study demonstrates a highly efficient regiodivergent ligand-controlled palladium-catalyzed cycloaddition reaction of vinyloxazolidine-2,4-diones with 1,3,5-triazinanes. In the presence diphosphine ligand, proceeds via (5+2) pathway to afford 1,3-diazepin-4-ones in excellent yields, while using monophosphine smoothly (3+2) give imidazolidin-4-ones good yields.

Language: Английский

Citations

9

Catalytic Enantioselective α-Allylation of Deconjugated Butenolides with Aza-π-allylpalladium 1,4-Dipoles: Access to Optically Pure 2-Piperidones Bearing an All-Carbon Quaternary Stereocenter DOI

Shu‐Pei Yuan,

Qing Bao,

Ting-Jia Sun

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(45), P. 8348 - 8353

Published: Nov. 10, 2022

A palladium-catalyzed enantioselective α-allylation of deconjugated butenolides with aza-π-allylpalladium 1,4-diploes, in situ generated from palladium-mediated decarboxylation cyclic carbamates and amide-substituted acyclic carbonates, has been successfully developed. An array enantioenriched 2-piperidones bearing an all-carbon quaternary stereocenter were obtained high yields excellent enantioselectivities (up to 99% yield ee). The utility this method was also showcased by a large-scale reaction synthetic transformations the product.

Language: Английский

Citations

29

Catalyst-Controlled Annulations of Strained Cyclic Allenes with π-Allylpalladium Complexes DOI
Dominick C. Witkowski, Matthew McVeigh, Georgia Scherer

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(19), P. 10491 - 10496

Published: May 4, 2023

Strained cyclic allenes are a class of in situ-generated fleeting intermediates that, despite being discovered more than 50 years ago, has received significantly less attention from the synthetic community compared to related strained intermediates. Examples trapping that involve transition metal catalysis especially rare. We report first annulations highly reactive with π-allylpalladium species. By varying ligand employed, either two isomeric polycyclic scaffolds can be obtained high selectivity. The products heterocyclic and sp3-rich bear or three new stereocenters. This study should encourage further development fragment couplings rely on for rapid assembly complex scaffolds.

Language: Английский

Citations

18

4-Vinylbenzodioxinones as a new type of precursor for palladium-catalyzed (4+3) cycloaddition of azomethine imines DOI
Yi Tang,

Rulei Zhang,

Yujie Dong

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(11), P. 1436 - 1439

Published: Jan. 1, 2024

Benzo-fused cyclic carbonates were designed and synthesized as a novel type of precursor π-allylpalladium zwitterionic intermediates.

Language: Английский

Citations

8

Palladium-Catalyzed Asymmetric Decarboxylation of 5-Vinyloxazolidine-2,4-Diones Triggering the Dearomatization of Electron-Deficient Indoles for the Synthesis of Chiral Highly Functionalized Pyrroloindolines DOI

Pei‐Hao Dou,

Xiaohui Fu, Yan Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3310 - 3315

Published: April 8, 2024

A catalyst system consisting of a chiral phosphoramidite ligand and Pd2(dba)3·CHCl3 causes the decarboxylation 5-vinyloxazolidine-2,4-diones to generate amide-containing aza-π-allylpalladium 1,3-dipole intermediates, which are capable triggering dearomatization 3-nitroindoles for diastereo- enantioselective [3+2] cycloaddition, leading formation series highly functionalized pyrroloindolines containing three contiguous stereogenic centers with excellent results (up 99% yield, 88:12 dr, 96% ee).

Language: Английский

Citations

6

Enantioselective Synthesis of Oxazocines via MQ‐Phos Enabled Palladium‐Catalyzed Asymmetric Formal [4+4]‐Cycloadditions DOI Creative Commons

Qingcheng Meng,

Yinggao Meng,

Qinglin Liu

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(31)

Published: June 17, 2024

Abstract Oxazocines are key structural intermediates in the synthesis of natural products and pharmaceutical molecules. However, oxazocines especially a highly enantioselective manner, is long‐standing formidable challenge due to unfavorable energetics involved cyclization. Herein, series new PNP‐Ligand P ‐chiral stereocenter first designed synthesized, called MQ‐Phos , successfully applied it Pd‐catalyzed higher‐order formal [4+4]‐cycloaddition α β ‐unsaturated imines with 2‐(hydroxymethyl)‐1‐arylallyl carbonates. The reaction features mild conditions, excellent regio‐ enantiocontrol broad substrate scope (54 examples). Various medium‐sized rings can be afforded moderate yields (up 92%) enantioselectivity 99% ee). newly developed critical for ring catalytic reactivity enantioselectivity.

Language: Английский

Citations

6