Divergent isoindolinone synthesis through palladium-catalyzed isocyanide bridging C–H activation DOI Creative Commons
Fulin Zhang,

Ruihua Zhao,

Lei Zhu

и другие.

Cell Reports Physical Science, Год журнала: 2022, Номер 3(3), С. 100776 - 100776

Опубликована: Фев. 16, 2022

The formation of thermodynamically accessible metallacycle is crucial to achieve site-selective C–H bond activation. Here, we report an isocyanide-bridging activation through the a five-membered palladacycle. As such, proximal in aldehyde moiety activated selectively. subsequent palladium shift and intramolecular C=N insertion construct valuable isoindolinone framework. Compared with conventional isocyanide-promoted activation, both carbon nitrogen atoms isocyanide are engaged new formations. Notably, three types isoindolinones can be obtained selectively by variations reaction conditions. Mechanistic studies shed light on pathways. Moreover, synthetic potential current methodology demonstrated providing concise routes key intermediates indoprofen, indobufen, aristolactams, lennoxamine, falipamil.

Язык: Английский

Palladium(II)-Catalyzed Annulative Difunctionalization of Two Inert C(sp3)–H Bonds by a Bifunctional Reagent DOI
Arghadip Ghosh, Nicolás Grimblat, Somratan Sau

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(11), С. 7627 - 7636

Опубликована: Май 22, 2023

Illustrated herein is a Pd(II)-catalyzed direct difunctionalization of two C(sp3)–H bonds aliphatic carboxylic acid derivatives by bifunctional reagents (BFRs) the 2-iodobenzoic series. The methyl 2-pyridyl sulfoximine (MPyS) bidentate directing group (DG), 2-chloro-5-trifluoromethylpyridine ligand, AgOAc as base, and NaBrO3 co-oxidant help concerted metalation deprotonation (CMD) inert bonds, well reductive elimination; density functional theory (DFT) studies shed light on these crucial steps. This process makes [C–C C–O] at gem-α,α′-di-Me groups in single operation, offering access to unusual benzo-fused peripheral-substituted caprolactones. transformation tolerates labile allows construction wide range caprolactones with structural diversity. Mechanistic reveal participation monomeric Pd species catalytic cycle. synthetic versatility complex molecular entities also presented.

Язык: Английский

Процитировано

14
Palladium-Catalyzed Annulations via Sequential C–H Activations of C(sp2)–H/C(sp3)–H or C(sp3)–H/C(sp3)–H Bonds DOI Creative Commons

Wan‐Xu Wei,

Mateusz Czajkowski,

Yangjin Kuang

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6535 - 6546

Опубликована: Апрель 15, 2024

Palladium-catalyzed C–H annulation reactions represent a compelling strategy to construct complex ring systems with high step economy. While there are many approaches annulate structures by activation of single bond, transformations that proceed multiple bonds less explored. This is especially true for examples where one the reacting located at an sp3 center. However, exciting developments in palladium-catalyzed continue expand scope these and provide innovative strategies challenging carbon–carbon bonds. From discoveries, sequential activations have emerged as powerful tool access through C(sp2)–H/C(sp3)–H or C(sp3)–H/C(sp3)–H In this Perspective, we showcase recent use order highlight synthetic potential activation-enabled annulations inspire future disconnections diverse scaffold synthesis.

Язык: Английский

Процитировано

6
β‐Diazocarbonyl Compounds: Synthesis and their Rh(II)‐Catalyzed 1,3 C−H Insertions DOI
Liyin Jiang, Zhaofeng Wang,

Melanie Armstrong

и другие.

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(11), С. 6177 - 6184

Опубликована: Дек. 4, 2020

Abstract Herein, we describe the first electrophilic diazomethylation of ketone silyl enol ethers with diazomethyl‐substituted hypervalent iodine reagents that gives access to unusual β‐diazocarbonyl compounds. The potential this unexplored class diazo compounds for development new reactions was demonstrated by discovery a rare Rh‐catalyzed intramolecular 1,3 C−H carbene insertion led complex cyclopropanes excellent stereocontrol.

Язык: Английский

Процитировано

37
Construction of Protoberberine Alkaloid Core through Palladium Carbene Bridging C–H Bond Functionalization and Pyridine Dearomatization DOI

Luoting Xin,

Wan Wan,

Yinghua Yu

и другие.

ACS Catalysis, Год журнала: 2021, Номер 11(3), С. 1570 - 1577

Опубликована: Янв. 19, 2021

Compounds with a pyridoisoquinolinone core often appear as members of the protoberberine alkaloid family. Traditional methods to construct this framework normally rely on manipulation sophisticated reactants. Herein, palladium-catalyzed reaction readily available pyridotriazoles and o-bromo/pseudohalo benzaldehydes is described, which provides modular approach derivatives. This methodology concise synthetic route prepare protoberberine-type alkaloids. The role pyridotriazole 2-fold, acting relay reagent promote C–H bond functionalization undergoing pyridine dearomatization polycyclic system.

Язык: Английский

Процитировано

32
A Cascade C(sp3)−H Annulation Involving C(alkyl),C(alkyl)‐Palladacycle Intermediates DOI Open Access
Liwei Zhou,

Xiahong Chen,

Qiong Peng

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Июль 25, 2024

Abstract C−H bond functionalization involving C , ‐palladacycle intermediates provides a unique platform for developing novel reactions. However, the vast majority of studies have been limited to transformations (aryl), ‐palladacycles. In sharp contrast, catalytic reactions (alkyl), (alkyl)‐palladacycles rarely reported. Herein, we disclose an unprecedented cascade C(sp 3 )−H annulation (alkyl)‐palladacycles. this protocol, alkene‐tethered cycloalkenyl bromides undergo intramolecular Heck/C(sp activation generate (alkyl)‐palladacycles, which can be captured by α ‐bromoacrylic acids afford tricyclic fused pyridinediones. addition, strategy also applied indole‐tethered construct pentacyclic pyridinediones via suquential Heck dearomatization/C(sp activation/decarboxylative cyclization. Notably, removal in reaction build interesting skeleton containing four‐membered ring. Preliminary mechanistic experiments indicate that five‐membered serve as key intermediates. Meanwhile, density functional theory (DFT) calculations provided insights into pathway.

Язык: Английский

Процитировано

5
Marine furanocembranoids-inspired macrocycles enabled by Pd-catalyzed unactivated C(sp3)-H olefination mediated by donor/donor carbenes DOI Creative Commons

Jiping Hao,

Xueying Guo, Shijun He

и другие.

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Фев. 26, 2021

Abstract Biomimetic modularization and function-oriented synthesis of structurally diversified natural product-like macrocycles in a step-economical fashion is highly desirable. Inspired by marine furanocembranoids, herein, we synthesize diverse alkenes substituted furan-embedded macrolactams via modular biomimetic assembly strategy. The success this the development crucial Pd-catalyzed carbene coupling between ene-yne-ketones as donor/donor precursors unactivated Csp 3 ‒H bonds which represents great challenge organic synthesis. Notably, method not only obviates use unstable, explosive, toxic diazo compounds, but also can be amenable to allenyl ketones precursors. DFT calculations demonstrate that formal 1,4-Pd shift could involved mechanism. Moreover, collected furanocembranoids-like show significant anti-inflammatory activities against TNF-α, IL-6, IL-1β cytotoxicity comparable Dexamethasone.

Язык: Английский

Процитировано

26
Regioselective synthesis of spirocyclic pyrrolines via a palladium-catalyzed Narasaka–Heck/C–H activation/[4 + 2] annulation cascade reaction DOI Creative Commons

Wan‐Xu Wei,

Xiangtao Kong,

Rui-Qiang Jiao

и другие.

Chemical Science, Год журнала: 2022, Номер 13(21), С. 6348 - 6354

Опубликована: Янв. 1, 2022

Readily available 2-chlorobenzoic acid or ethyl phenylpropiolate as the C2 insertion unit. High regioselectivity. Broad substrate scope. Mechanistic studies.

Язык: Английский

Процитировано

19
Tunable Construction of Multisubstituted 1,3-Dienes and Allenes via a 1,4-Palladium Migration/Carbene Insertion Cascade DOI
Jie Lin, Zilong Huang, Juan Ma

и другие.

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(18), С. 12019 - 12035

Опубликована: Сен. 2, 2022

Efficient palladium-catalyzed vinylic C-H alkenylation and allenylation of gem-disubstituted ethylenes with N-tosylhydrazones aryl alkyl diaryl ketones were achieved to access trisubstituted 1,3-dienes tetrasubstituted allenes, respectively. An vinyl 1,4-palladium migration/carbene insertion/β-hydride elimination sequence proceeded switch the chemo- regioselectivities give structurally diverse products. Use 2-FC6H4OH additive enables enhancement reaction efficiency through accelerating key migration process.

Язык: Английский

Процитировано

18
Regioselective C–H Active Carbonylation via 1,4-Palladium Migration DOI
Ming Li,

Shun‐Xi Li,

Dong‐Ping Chen

и другие.

Organic Letters, Год журнала: 2023, Номер 25(16), С. 2761 - 2766

Опубликована: Апрель 13, 2023

We report a highly regioselective three-component coupling reaction of styrene, CO gas, and an amine compound to synthesize multisubstituted α,β-unsaturated amides, which involves palladium-catalyzed sequential 1,4-palladium migration, C(sp2)-H activation, carbonylation, amination. Salient features this strategy include the use 1 atm CO, excellent stereochemistry, good functional group tolerance. Further, series control experiments density theory calculations were performed afford some insights for transfer mechanism.

Язык: Английский

Процитировано

11
1,4-Pd Migration-Enabled Synthesis of Fused 4-Membered Rings DOI Creative Commons

Μαρία Τσιτοπούλου,

Antonin Clemenceau, Pierre Thesmar

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18811 - 18816

Опубликована: Июль 5, 2024

1,4-Palladium migration has been widely used for the functionalization of remote C–H bonds. However, this mechanism limited to aryl halide precursors. This work reports an unprecedented Pd0-catalyzed cyclobutanation protocol producing valuable fused cyclobutanes starting from cycloalkenyl (pseudo)halides. reaction takes place via alkenyl-to-alkyl 1,4-Pd migration, followed by intramolecular Heck coupling. The method performs best with cyclohexenyl precursors, giving access a variety substituted bicyclo[4,2,0]octenes. Reactants containing N-methyl or methoxy group give rise azetidines oxetanes, respectively, same mechanism. Kinetic and deuterium-labeling studies point rate-limiting C(sp3)–H activation step.

Язык: Английский

Процитировано

4