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

Transition‐Metal‐Catalyzed Annulations Involving the Activation of C(sp3)−H Bonds DOI
Marc Font, Moisés Gulı́as, José L. Mascareñas

и другие.

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(6)

Опубликована: Окт. 26, 2021

The selective functionalization of C(sp

Язык: Английский

Процитировано

66

Tandem Reactions involving 1,4‐Palladium Migrations DOI
Mengyao Li, Dong Wei, Chen‐Guo Feng

и другие.

Chemistry - An Asian Journal, Год журнала: 2022, Номер 17(15)

Опубликована: Июнь 6, 2022

Abstract Transition‐metal‐catalyzed tandem reactions have become a mainstay in organic chemistry owing to their high atom‐ and step‐economies. Metal‐migration‐based allow the engagement of simple starting materials for incorporating functional groups into certain positions constructing complex scaffolds, which provide novel means that are complementary traditional cross‐coupling or C−H activation processes. In light broad utility 1,4‐Pd migration reaction, this paper reviews its progress past two decades, summarizing process classifying it based on insertion, elimination, transmetalation, bond activation. Special emphasis is placed driving force Pd different mechanisms. Moreover, review also attempts summarize common strategies improving regio‐ site‐selectivities process.

Язык: Английский

Процитировано

44

Palladium-Catalyzed [3 + 2] Annulation of Aromatic Amides with Maleimides through Dual C–H Activation DOI

Gouranga Naskar,

Masilamani Jeganmohan

Organic Letters, Год журнала: 2023, Номер 25(13), С. 2190 - 2195

Опубликована: Март 26, 2023

A palladium-catalyzed [3 + 2] annulation of substituted aromatic amides with maleimides providing tricyclic heterocyclic molecules in good to moderate yields through weak carbonyl chelation is reported. The reaction proceeds via a dual C-H bond activation where the first takes place selectively at benzylic position followed by second meta afford five-membered cyclic ring. An external ligand Ac-Gly-OH has been used succeed this protocol. plausible mechanism proposed for reaction.

Язык: Английский

Процитировано

29

Experimental and Computational Studies of Palladium-Catalyzed Spirocyclization via a Narasaka–Heck/C(sp3 or sp2)–H Activation Cascade Reaction DOI

Wan‐Xu Wei,

Yuke Li, Yating Wen

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(20), С. 7868 - 7875

Опубликована: Май 11, 2021

The first synthesis of highly strained spirocyclobutane-pyrrolines via a palladium-catalyzed tandem Narasaka-Heck/C(sp3 or sp2)-H activation reaction is reported here. key step in this transformation the δ-C-H bond an situ generated σ-alkyl-Pd(II) species to form five-membered spiro-palladacycle intermediate. concerted metalation-deprotonation (CMD) process, rate-determining step, and energy barrier entire were explored by density functional theory (DFT) calculations. Moreover, series control experiments was conducted probe reversibility C(sp3)-H step.

Язык: Английский

Процитировано

43

Reversible C–C bond formation using palladium catalysis DOI
Austin D. Marchese, Bijan Mirabi, Colton E. Johnson

и другие.

Nature Chemistry, Год журнала: 2022, Номер 14(4), С. 398 - 406

Опубликована: Март 17, 2022

Язык: Английский

Процитировано

38

Remote Construction of N‐Heterocycles via 1,4‐Palladium Shift‐Mediated Double C−H Activation DOI Creative Commons
Takeru Miyakoshi, Nadja Niggli, Olivier Baudoin

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(17)

Опубликована: Фев. 10, 2022

Abstract In the past years, Pd 0 ‐catalyzed C(sp 3 )−H activation provided efficient and step‐economical methods to synthesize carbo‐ heterocycles via direct 2 )−C(sp ) bond formation. We report herein that a 1,4‐Pd shift allows access N‐heterocycles which are difficult build reaction. It is shown o ‐bromo‐ N ‐methylanilines undergo at ‐methyl group, followed by intramolecular trapping or another nitrogen substituent remote C−C formation generate biologically relevant isoindolines β‐lactams. The product selectivity influenced employed ligand, with NHCs favoring of coupling against products arising from N‐demethylation.

Язык: Английский

Процитировано

34

Diastereoselective palladium-catalyzed functionalization of prochiral C(sp3)–H bonds of aliphatic and alicyclic compounds DOI
Srinivasarao Arulananda Babu,

Yashika Aggarwal,

Pooja Patel

и другие.

Chemical Communications, Год журнала: 2022, Номер 58(16), С. 2612 - 2633

Опубликована: Янв. 1, 2022

Advancements in the palladium-catalyzed functionalization of diastereotopic or prochiral C(sp 3 )–H bonds generating stereogenic centers and stereo-arrays aliphatic compounds have been highlighted.

Язык: Английский

Процитировано

33

Advances in Palladium-Catalyzed C(sp3)–H Functionalization: The Role of Traceless Directing Groups DOI
Masoud Sadeghi

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 15356 - 15373

Опубликована: Окт. 3, 2024

Язык: Английский

Процитировано

8

Pd-Catalyzed ipso,meta-Dimethylation of ortho-Substituted Iodoarenes via a Base-Controlled C–H Activation Cascade with Dimethyl Carbonate as the Methyl Source DOI
Zhuo Wu, Wei Feng,

Bin Wan

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(12), С. 4524 - 4530

Опубликована: Март 22, 2021

A methyl group can have a profound impact on the pharmacological properties of organic molecules. Hence, developing methylation methods and methylating reagents is essential in medicinal chemistry. We report palladium-catalyzed dimethylation reaction ortho-substituted iodoarenes using dimethyl carbonate as source. In presence K2CO3 base, are dimethylated at ipso- meta-positions iodo group, which represents novel strategy for meta-C–H methylation. With KOAc subsequent oxidative C(sp3)–H/C(sp3)–H coupling occurs; this case, overall transformation achieves triple C–H activation to form three new C–C bonds. These reactions allow expedient access 2,6-dimethylated phenols, 2,3-dihydrobenzofurans, indanes, ubiquitous structural motifs synthetic intermediates biologically pharmacologically active compounds.

Язык: Английский

Процитировано

37

Alkyne Insertion Enabled Vinyl to Acyl 1,5‐Palladium Migration: Rapid Access to Substituted 5‐Membered‐Dihydrobenzofurans and Indolines DOI

Mingruo Ding,

Pengcheng Ou,

Xuening Li

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(18)

Опубликована: Фев. 21, 2023

"Through space" palladium/hydrogen shift is an efficient strategy to achieve selective functionalization of a specific remote C-H bond. Compared with relatively extensive exploited 1,4-palladium migration process, the relevant 1,5-Pd/H was far less investigated. We herein report novel pattern between vinyl and acyl group. Through pattern, rapid access 5-membered-dihydrobenzofuran indoline derivatives has been achieved. Further studies have unveiled unprecedented trifunctionalization (vinylation, alkynylation amination) phenyl ring through 1,5-palladium relayed decarbonylative Catellani type reaction. A series mechanistic investigations DFT calculations provided insights into reaction pathway. Notably, it that in our case prefers stepwise mechanism involving PdIV intermediate.

Язык: Английский

Процитировано

17