Ir-catalyzed chemoselective reduction of β-amido esters: A versatile approach to β-enamino esters

Yang, Zhiping; Lu, Guangyuan; Ye, Jian‐Liang; Huang, Pei‐Qiang

doi:10.1016/j.tet.2018.12.024

Cited by 11 publications

(2 citation statements)

References 79 publications

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“…57 In 2019, Huang and Ye reported the use of Vaska's complex and TMDS to chemoselectively reduce β-amido esters to give β-enamino esters (Scheme 13). 58 In addition, cyclic βamido esters were also reduced in this system to give endocyclic β-enamino esters; however, acyclic β-amido ketones were not reduced under the reaction conditions. The βenamino ester products were utilized in a Pd-catalyzed intramolecular oxidative cyclization, showcasing their utility as synthetic intermediates.…”

Section: Recent Applications In the Synthesis Ofmentioning

confidence: 99%

Catalytic Reductive Functionalization of Tertiary Amides using Vaska’s Complex: Synthesis of Complex Tertiary Amine Building Blocks and Natural Products

et al. 2020

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The tertiary amide is a ubiquitous functional group and plays an irreplaceable role in medicinal chemistry. Its robust nature has meantin the pastthat selective manipulation of this motif remained elusive. The reductive activation through hydrosilylation of tertiary amidesusing Vaska’s complex (IrCl(CO)(PPh3)2)has emerged as a powerful strategy for the chemoselective transformation of amides into reactive enamines and iminium ions. Furthermore, these synthetically valuable species can be accessed in the presence of traditionally more reactive functional groups. This approach to amide reductive activation via hydrosilylation has been exploited in a range of downstream C–C bond forming processes and has seen significant applications in total synthesis, enabling streamlined routes for the synthesis of complex natural product architectures. This perspective covers the development of this synthetic strategy, from initial hydrosilylation studies to its flourishing use in the reductive functionalization of amide-containing molecules, both simple and complex.

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Section: Recent Applications In the Synthesis Ofmentioning

confidence: 99%

Catalytic Reductive Functionalization of Tertiary Amides using Vaska’s Complex: Synthesis of Complex Tertiary Amine Building Blocks and Natural Products

et al. 2020

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“…An intriguing feature of the iridium-catalyzed reaction is that further reaction of the silylhemiaminal induces elimination of silanol to give enamines. In some cases involving an intermediate that forms π-conjugated enamines, silylhemiaminal is stable enough to isolate, to obtain spectroscopy on, and to use as synthetic intermediates for further transformations …”

Section: Conclusion and Remarksmentioning

confidence: 99%

Donor–Acceptor π-Conjugated Enamines: Functional Group-Compatible Synthesis from Amides and Their Photoabsorption and Photoluminescence Properties

Tahara¹,

Kitahara

Sakata

et al. 2019

J. Org. Chem.

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High functional group compatibility of iridium-catalyzed synthesis of enamines from amides and 1,1,3,3-tetramethyldisiloxane (TMDS) realized facile access of a series of donor (D)−π–acceptor (A)-conjugated enamines, in which enamine behaves as a donor functional group. The amide precursors containing reducible functional groups, such as halogen, carbonyl, and nitro groups, underwent reaction with TMDS to give the corresponding enamines in high yields. In most cases, chemoselective hydrosilane reduction of the amide group occurred while other reducible groups remained intact. Absorption and emission properties including solvatochromic behavior for the resulting D−π–A-conjugated enamines were determined using UV–visible and fluorescent spectra, which provided an understanding of the donor properties of the CHCHNPh2 group and photofunctional properties of the D−π–A conjugated enamines as a fluorescent dye. Maximum absorption wavelength (λabs) of p-ZC6H4CHCHNPh2 was predictable from λabs of p-ZC6H4NPh2, which was supported by density functional theory calculations. Some of the D−π–A-conjugated enamines showed fluorescence with moderate fluorescence quantum yields (Φfl). Of interest are unusually emissive π-conjugated enamines containing a nitro group, which generally behaves as strong quenchers of fluorescence. The additive effect of B(C6F5)3 resulted in significant red shifts of λabs and λfl. In some cases, high Φfl was observed in the solution state.

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Hypervalent Iodine‐Mediated and Traceless Fluorine‐Oriented: Synthesis of 5‐Methyl‐1,2,3,4‐tetrahydropyridine from Unactivated Alkenes

et al. 2021

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An original metal‐free method for the convenient preparation of 5‐methyl‐1,2,3,4‐tetrahydropyridine derivatives from simple unactivated alkenes was firstly developed with excellent yields under mild conditions, based on hypervalent iodine compounds in combination with boron fluoride reagents. Mechanism studies have shown that fluorine participates in the reaction as a traceless guiding group, ensuring the successful construction of the Csp2−N bond of tetrahydropyridine derivatives via the selective intramolecular coupling reaction of unactivated alkenes.

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Ir-catalyzed chemoselective reduction of β-amido esters: A versatile approach to β-enamino esters

Cited by 11 publications

References 79 publications

Catalytic Reductive Functionalization of Tertiary Amides using Vaska’s Complex: Synthesis of Complex Tertiary Amine Building Blocks and Natural Products

Catalytic Reductive Functionalization of Tertiary Amides using Vaska’s Complex: Synthesis of Complex Tertiary Amine Building Blocks and Natural Products

Donor–Acceptor π-Conjugated Enamines: Functional Group-Compatible Synthesis from Amides and Their Photoabsorption and Photoluminescence Properties

Hypervalent Iodine‐Mediated and Traceless Fluorine‐Oriented: Synthesis of 5‐Methyl‐1,2,3,4‐tetrahydropyridine from Unactivated Alkenes

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