Iridium‐Catalyzed Intermolecular Asymmetric Allylic Amination with Pyridones

Tu, Hang-Fei; Nie, Yu-Han; Zheng, Chao; You, Shu‐Li

doi:10.1002/adsc.202200347

Cited by 12 publications

(4 citation statements)

References 92 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[32] Recently, You's group employed an iridium-catalyzed Nallylation of 2-hydroxypyridines reaction in the kinetic resolution of branched allyl alcohols (Scheme 13). [33] Using [Ir(cod)Cl] 2 / Carreira ligand L6 as catalyst and Zn(OTf) 2 as additive, this kinetic resolution reaction occurred smoothly. The desired αchiral N-allylic pyridones 52 were delivered with up to 42 % yield and 99 % ee, while highly enantioenriched allylic alcohols (R)-51 were recovered.…”

Section: N-allylation Of 2-hydroxypyridinesmentioning

confidence: 93%

2‐Hydroxypyridines as N‐ and O‐Nucleophiles in Organic Synthesis

Li,

Wang,

2023

Eur J Org Chem

View full text Add to dashboard Cite

2‐Hydroxypyridines have emerged as versatile nucleophiles in organic synthesis. The N‐ and O‐functionalization of 2‐hydroxypyridines affords straightforward and practical methods for the construction of N‐substituted 2‐pyridones and O‐substituted 2‐hydroxypyridines, which are important structural motifs in numerous natural products, pharmaceuticals and biologically active compounds. Nonetheless, the competition between N‐ and O‐functionalization of 2‐hydroxypyridines presents an inevitable and formidable challenge. In the past few decades, chemoselective N‐ and/or O‐functionalization of 2‐hydroxypyridines has received extensive attention from the synthetic community, resulting in the development of elegant and effective strategies to address this chemoselectivity. This review provides a summary of recent advancements in the realm of transition‐metal and organo‐catalyzed, as well as visible‐light promoted chemoselective functionalization of 2‐hydroxypyridines, including N‐alkylation, N‐allylation, N‐arylation, N‐alkenylation, O‐alkylation, O‐allylation, O‐arylation, and O‐alkenylation.

show abstract

Section: N-allylation Of 2-hydroxypyridinesmentioning

confidence: 93%

2‐Hydroxypyridines as N‐ and O‐Nucleophiles in Organic Synthesis

Li,

Wang,

2023

Eur J Org Chem

View full text Add to dashboard Cite

show abstract

“…An analogous iridium-catalyzed intermolecular asymmetric allylic amination was developed for 4- and 2-hydroxypyridines 1 with allylic alcohols 335 to render N -allylated 2-pyridones and 4-pyridones 337 in good yields with excellent enantioselectivities ( Scheme 159 ). 228 Mechanistic studies indicated that the reaction was a kinetic resolution process and it displayed a broad substrate scope for both pyridines and allylic alcohols. Moreover, the reaction was successfully performed on a gram-scale and the amination product was further derivatized to prove the practicality of this method.…”

Section: Addition Of Other Nucleophilesmentioning

confidence: 99%

Recent Strategies in the Nucleophilic Dearomatization of Pyridines, Quinolines, and Isoquinolines

Escolano,

Gaviña,

Alzuet-Piña

et al. 2024

Chem. Rev.

View full text Add to dashboard Cite

Dearomatization reactions have become fundamental chemical transformations in organic synthesis since they allow for the generation of three-dimensional complexity from two-dimensional precursors, bridging arene feedstocks with alicyclic structures. When those processes are applied to pyridines, quinolines, and isoquinolines, partially or fully saturated nitrogen heterocycles are formed, which are among the most significant structural components of pharmaceuticals and natural products. The inherent challenge of those transformations lies in the low reactivity of heteroaromatic substrates, which makes the dearomatization process thermodynamically unfavorable. Usually, connecting the dearomatization event to the irreversible formation of a strong C−C, C− H, or C−heteroatom bond compensates the energy required to disrupt the aromaticity. This aromaticity breakup normally results in a 1,2-or 1,4-functionalization of the heterocycle. Moreover, the combination of these dearomatization processes with subsequent transformations in tandem or stepwise protocols allows for multiple heterocycle functionalizations, giving access to complex molecular skeletons. The aim of this review, which covers the period from 2016 to 2022, is to update the state of the art of nucleophilic dearomatizations of pyridines, quinolines, and isoquinolines, showing the extraordinary ability of the dearomative methodology in organic synthesis and indicating their limitations and future trends.

show abstract

“…The catalyst system was made by an iridium complex with Carreira's [P/olefin] ligand L12 with the necessary inclusion of a Lewis acid such as Zn(OTf)2. The reaction obtained the corresponding allylated pyridines of type 98 with excellent chemo-, regio-and enantioselectivities (>19:1 N/O, >19/1 branch/linear and ≥89% ee) (Scheme 32) [78]. Scheme 32.…”

Section: Scheme 24 Palladium-catalyzed Asymmetric Allylation Of 2-hyd...mentioning

confidence: 99%

Recent Progresses in the Catalytic Stereoselective Dearomatization of Pyridines

Comparini,

Pineschi

2023

Molecules

View full text Add to dashboard Cite

1,2- and 1,4-dihydropyridines and N-substituted 2-pyridones are very important structural motifs due to their synthetic versatility and vast presence in a variety of alkaloids and bioactive molecules. In this article, we gather and summarize the catalytic and stereoselective synthesis of partially hydrogenated pyridines and pyridones via the dearomative reactions of pyridine derivatives up to mid-2023. The material is fundamentally organized according to the type of reactivity (electrophilic/nucleophilic) of the pyridine nucleus. The material is further sub-divided taking into account the nucleophilic species when dealing with electrophilic pyridines and considering the reactivity manifold of pyridine derivatives behaving as nucleophiles at the nitrogen site. The latter more recent approach allows for an unconventional entry to chiral N-substituted 2- and 4-pyridones in non-racemic form.

show abstract

Iridium‐Catalyzed Intermolecular Asymmetric Allylic Amination with Pyridones

Cited by 12 publications

References 92 publications

2‐Hydroxypyridines as N‐ and O‐Nucleophiles in Organic Synthesis

2‐Hydroxypyridines as N‐ and O‐Nucleophiles in Organic Synthesis

Recent Strategies in the Nucleophilic Dearomatization of Pyridines, Quinolines, and Isoquinolines

Recent Progresses in the Catalytic Stereoselective Dearomatization of Pyridines

Contact Info

Product

Resources

About