Enantioselective β-C(sp3)–H Nucleophilic Tosylation of Native Amides: A Synthetic Platform for Chiral Methyl Stereocenters DOI
Yuxin Ouyang, D. Quang Phan, Nikita Chekshin

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 31, 2025

Enantioselective oxygenation of unactivated C(sp3)-H bonds via asymmetric metalation remains an unsolved challenge. Herein we report the development a Pd-catalyzed, enantioselective tosylation native amides with NaOTs as nucleophile, representing rare example C-H functionalization nucleophilic coupling partner. High enantioselectivity in this reaction is achieved by chiral monoprotected amino sulfonamide (MPASA) ligands. Substantial enhancement silver salt additives was also observed. Through desymmetrization readily available isopropyl moiety, structurally diverse β-tosylated bearing α-methyl stereocenter were obtained high yield and enantioselectivity, which complements current enzymatic method for making Roche ester synthon. The tosylated products are highly versatile building blocks further diversifications nitrogen, oxygen, other nucleophiles, thus providing platform constructing methyl stereocenters.

Язык: Английский

Synthesis of γ-Lactams via Palladium-Catalyzed C(sp3)–H Bond Activation of Alkyl Sulfonamides with Substituted Alkenes DOI
Ananya Dutta, Masilamani Jeganmohan

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 20, 2025

A methodology for the γ-butyrolactam scaffolds via ligand-enabled C(sp3)–H bond functionalization of sulfonamides with olefins has been demonstrated. The protocol found to be compatible several activated and unactivated olefins, desired lactams were formed in excellent yields. plausible mechanism described account lactamization reaction as well supported by mechanistic investigation including a 1H NMR study isolation palladacycle intermediate.

Язык: Английский

Процитировано

0

Palladium-Catalyzed Directed Alkenylation of Alkyl Amides with Unactivated Alkenes: Access to γ-Alkenyl γ-Lactams DOI

Madhab Barman,

Santu Mandal, Maniya V. Nanjegowda

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 13, 2025

Pd(II)-catalyzed cascade C(sp3)–H alkenylation and cyclization of alkyl amides with readily accessible unactivated alkenes have been accomplished. Alkenylation subsequent intramolecular empowered the formation functionalized γ-lactams, which present as an active core several bioactive natural products. The use catalytic Cu(OAc)2 along molecular oxygen oxidant, a 2-chloropyridine ligand, site selectivity, substrate scope, gram-scale synthesis are important practical features.

Язык: Английский

Процитировано

0

Synthesis of lactones and lactams via C(sp3)–H bond functionalization DOI

E. Premkumar,

Ramdas Sreedharan,

Premananda Ghosh

и другие.

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

In this review, we have showcased the diverse aspects of transition-metal catalysis, biocatalysis, and photocatalytic C(sp 3 )–H bond functionalization to access lactones lactams.

Язык: Английский

Процитировано

0

Enantioselective β-C(sp3)–H Nucleophilic Tosylation of Native Amides: A Synthetic Platform for Chiral Methyl Stereocenters DOI
Yuxin Ouyang, D. Quang Phan, Nikita Chekshin

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 31, 2025

Enantioselective oxygenation of unactivated C(sp3)-H bonds via asymmetric metalation remains an unsolved challenge. Herein we report the development a Pd-catalyzed, enantioselective tosylation native amides with NaOTs as nucleophile, representing rare example C-H functionalization nucleophilic coupling partner. High enantioselectivity in this reaction is achieved by chiral monoprotected amino sulfonamide (MPASA) ligands. Substantial enhancement silver salt additives was also observed. Through desymmetrization readily available isopropyl moiety, structurally diverse β-tosylated bearing α-methyl stereocenter were obtained high yield and enantioselectivity, which complements current enzymatic method for making Roche ester synthon. The tosylated products are highly versatile building blocks further diversifications nitrogen, oxygen, other nucleophiles, thus providing platform constructing methyl stereocenters.

Язык: Английский

Процитировано

0