Catalytic Azido‐Hydrazination of Alkenes Enabled by Visible Light: Mechanistic Studies and Synthetic Applications

Wang, Peng; Luo, Yunxuan; Zhu, Songsong; Lu, Dengfu; Gong, Yuefa

doi:10.1002/adsc.201901041

Cited by 22 publications

(14 citation statements)

References 83 publications

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“…To further explore the reactivity of the intermediate hydrazinium salt 14 , its use in the asymmetric synthesis of heterocycles was briefly evaluated. Under conditions reported, 17 ( S )- 14 was smoothly converted into pyrazole ( S )- 15 and 1,2-dihydropyridazine-3,6-dione ( S )- 16 (Scheme 4 ). In an identical manner, use of ( R )- 14 gave ( R )- 15 and ( R )- 16 .…”

Section: Resultsmentioning

confidence: 99%

Asymmetric Synthesis of γ-Amino-Functionalised Vinyl Sulfones: De Novo Preparation of Cysteine Protease Inhibitors

Evans¹,

Shen²,

Cunningham³

2022

Synthesis

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The enantioselective azo-based α-amination of an aldehyde followed by a Horner–Wadsworth–Emmons-based vinyl sulfone formation is reported. The thus obtained optically active N,N′-diprotected trans-(phenylsulfonyl)vinyl hydrazine products were then converted into the corresponding N-functionalised trans-(phenylsulfonyl)vinyl amines. Specifically, reaction of 4-phenylbutanal with di-tert-butyl azodicarboxylate (DBAD) in the presence of l- or d-proline, followed by addition of diethyl [(phenylsulfonyl)methyl]phosphonate, gave either enantiomer of di-tert-butyl trans-1-[5-phenyl-1-(phenylsulfonyl)pent-1-en-3-yl]hydrazine-1,2-dicarboxylate. The enantiomeric excesses of the (+)- and (–)-enantiomers prepared in this manner were in the range 86–89%. The conversion of these γ-hydrazino vinyl sulfones into the corresponding γ-amino-substituted compounds was achieved following a Boc deprotection, Zn reduction, N-functionalisation sequence. This three-step sequence was reasonably efficient (approx. 50%) and no erosion of enantiopurity was found to have taken place. The compounds accessed via this process include both enantiomers of tert-butyl trans-[5-phenyl-1-(phenylsulfonyl)pent-1-en-3-yl]carbamate and epimeric dipeptide mimetics including 4-methyl-N-{(S)-1-oxo-3-phenyl-1-[((S,E)-5-phenyl-1-(phenylsulfonyl)pent-1-en-3-yl)amino]propan-2-yl}piperazine-1-carboxamide (also known as K777).

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Section: Resultsmentioning

confidence: 99%

Asymmetric Synthesis of γ-Amino-Functionalised Vinyl Sulfones: De Novo Preparation of Cysteine Protease Inhibitors

Evans¹,

Shen²,

Cunningham³

2022

Synthesis

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“…In the presence of visible-light the exited Ir-catalyst induce the reductive cleavage of reactant (A) to generate a radical (B) and a carboxylate anion. The N-centered radical (B) adds to the styrene (33) to produce an alkyl radical intermediate (C) with the regeneration of photocatalyst Ir III via oxidation to give a carbocation intermediate (D). In CH 3 CN, (D) is trapped by the solvent to give a nitrilium intermediate (E) through a Ritter-type process.…”

Section: Ir-catalyzed C-n Bond Formationsmentioning

confidence: 99%

“…Wang et al in 2019 depicted a visible-light-induce intermolecular azidohydrazination method for the synthesis of β-azido alkyl hydrazines (50) from unactivated alkenes (49)(Figure 29) [33]. This transformation occurs via metalfree and redox neutral conditions and applies to a wide range of alkenes.…”

Section: Rose Bengal and 9-fluorenone Catalyzed C-n Bond Formationmentioning

confidence: 99%

Construction of C-N Bond via Visible-Light-Mediated Difunctionalization of Alkenes

Patel¹,

Alam²,

Rakshit³

2021

Alkenes - Recent Advances, New Perspectives and Applications

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In the last few years, the photo-redox process via single-electron transfer (SET) has received substantial attention for the synthesis of targeted organic compounds due to its environmental friendliness and sustainability. Of late visible-light-mediated difunctionalization of alkenes has gained much attention because of its step economy, which allows the consecutive installation of two functional groups across the C=C bond in a single operation. The construction of N-containing compounds has always been important in organic synthesis. Molecules containing C-N bonds are found in many building blocks and are important precursors to other functional groups. Meanwhile, C-N bond formation via the addition of the C=C double bond is gaining prominence. Therefore, considering the influence and synthetic potential of the C-N bond, here we provide a summary of the state of the art on visible-light-driven difunctionalizations of alkene. We hope that the construction of the C-N bond via visible-light-mediated difunctionalization of alkenes will be useful for medicinal and synthetic organic chemists and will inspire further reaction development in this interesting area.

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“…In spite of the advances in related non‐asymmetric reactions, [21a–k, 23] enantioselective aminoazidation and diazidation are underdeveloped. There is only one example of a successful enantioselective aminoazidation, an intra/ intermolecular aminoazidation leading to structurally diverse substituted piperidines (Scheme 1 c).…”

Section: Introductionmentioning

confidence: 99%

Iron‐Catalyzed Radical Asymmetric Aminoazidation and Diazidation of Styrenes

Sun

Zhou

et al. 2021

Angewandte Chemie

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Asymmetric aminoazidation and diazidation of alkenes are straightforward strategies to build value‐added chiral nitrogen‐containing compounds from feedstock chemicals. They provide direct access to chiral organoazides and complement enantioselective diamination. Despite the advances in non‐asymmetric reactions, asymmetric aminoazidation or diazidation based on acyclic systems has not been previously reported. Here we describe the iron‐catalyzed intermolecular asymmetric aminoazidation and diazidation of styrenes. The method is practically useful and requires relatively low loading of catalyst and chiral ligand. With mild reaction conditions, the reaction can be completed on a 20 mmol scale. Studies of the mechanism suggest that the reaction proceeds via a radical pathway and involves stereocontrol of an acyclic free radical which probably takes place through a group transfer mechanism.

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Catalytic Azido‐Hydrazination of Alkenes Enabled by Visible Light: Mechanistic Studies and Synthetic Applications

Cited by 22 publications

References 83 publications

Asymmetric Synthesis of γ-Amino-Functionalised Vinyl Sulfones: De Novo Preparation of Cysteine Protease Inhibitors

Asymmetric Synthesis of γ-Amino-Functionalised Vinyl Sulfones: De Novo Preparation of Cysteine Protease Inhibitors

Construction of C-N Bond via Visible-Light-Mediated Difunctionalization of Alkenes

Iron‐Catalyzed Radical Asymmetric Aminoazidation and Diazidation of Styrenes

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