The regioselective Wacker oxidation of internal allylamines: synthesis of functionalized and challenging β-amino ketones

Abstract

A convenient and general protocol for the palladium-catalysed oxidation of internal allylamine derivatives to β-amino ketones is reported. The transformation occurs at room temperature and shows wide substrate scope as...

Base mediated aza-[2 + 1] annulation and regioselective aziridine ring-opening cascade: mild synthesis of functionalized β-amino ketones from cyclic N-sulfonyl aldimines and α-carbonyl sulfonium salts

“… 3 In addition, aza-Michael addition reaction of α , β -unsaturated ketones with amine-based nucleophiles represent another reliable protocol to access β -AKs motifs. 4 In parallel, transition metal-catalyzed reactions, such as coper-catalyzed decarboxylative Mannich reaction, 5 palladium-catalyzed aminocarbonylation, 6 rhodium-catalyzed hydrogenation of β -ketoenamides, 7 and palladium-catalyzed Tsuji–Wacker oxidation of internal allylamines, 8 have been also successfully employed in preparing structurally diverse and synthetically useful β -AKs and their related analogues. Despite great advances have been made for such molecule synthesis, most of those methodologies usually required the use of corresponding pre-functionalized substrates, expensive catalysts, and harsh reaction conditions.…”

Synthesis of Chiral α‐Amino Ketones via Transition Metal Catalyzed or Photoredox Cross‐Coupling and Olefin Photo‐Cleavage Reaction Sequence

“…While the scientific community has devoted substantial efforts to both traditional α‐AK synthesis and the metallaphotoredox approach, new protocols and techniques to synthesize these biologically relevant motifs from readily accessible starting materials are always needed and remain a significant challenge to synthetic chemists. Recently, we reported a straightforward and modular approach for the preparation of β‐amino ketones that involved a combination of dual photoredox/Ni‐catalysed cross‐coupling of 3‐bromo allylamines or 3‐bromo allyl alcohols with alkyl bromides followed by regioselective Wacker oxidation [22] . The remarkable chemoselectivity and high functional group tolerance of the initial photoredox cross‐coupling step allowed for simple and rapid structural diversification of the starting molecular core just by varying the electrophilic cross partner.…”

“…Recently, we reported a straightforward and modular approach for the preparation of βamino ketones that involved a combination of dual photoredox/Ni-catalysed cross-coupling of 3-bromo allylamines or 3-bromo allyl alcohols with alkyl bromides followed by regioselective Wacker oxidation. [22] The remarkable chemoselectivity and high functional group tolerance of the initial photoredox cross-coupling step allowed for simple and rapid structural diversification of the starting molecular core just by varying the electrophilic cross partner.…”

Sustainable continuous flow synthesis of β-aminocarbonyls via acid-catalyzed hydration of N-Boc-2-azetines

“…β-Aminocarbonyl compounds serve as valuable building blocks in the synthesis of biologically and medicinally significant molecules. 1–3 These compounds are also privileged scaffolds in the field of peptidomimetics and molecular recognition. 4 In fact, β-aminocarbonyl compounds are valuable intermediates in organic synthesis, especially in the production of β-amino alcohols, 5 β-amino acids, 6 and lactams, 7 which are crucial in various pharmaceutical and natural product synthesis.…”

“…Calculated by1 HNMR on the crude reaction mixture. b Isolated yield.Reaction Chemistry & Engineering PaperThis journal is © The Royal of Chemistry 2023ConclusionsIn our study reports an unprecedented preparation of β-aminocarbonyls via hydration of N-Boc-2azetines promoted by acid catalysis.…”