A Visible-Light-Induced α-Aminoalkyl-Radical-Mediated Halogen-Atom Transfer Process: Modular Synthesis of Phenanthridinone Alkaloids

Mondal, Karunamayee; Mallik, Sumitava; Sardana, Sunaina; Baidya, Mahiuddin

doi:10.1021/acs.orglett.3c00358

Cited by 12 publications

(7 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thus, on the basis of the aryl-halogen and Me 3 Sn-Halogen BDE values available, [15] the generated Me 3 Sn * arising from path b [32] could be able to generate the aryl radical Ar * via a halogen atom transfer (XAT) step (path c'). [34][35][36][37] In this case, the formation of a strong Me 3 Sn-halogen bond [15] has a key role as the driving force of the process.…”

Section: Resultsmentioning

confidence: 99%

“…However, the surprising reactivity of poorly reducible aryl halides (including, although with low efficiency, aryl chlorides, see Table 1) [29,33] pushed to consider an alternative mechanistic pathway. Thus, on the basis of the aryl‐halogen and Me 3 Sn‐Halogen BDE values available, [15] the generated Me 3 Sn⋅ arising from path b [32] could be able to generate the aryl radical Ar⋅ via a halogen atom transfer (XAT) step (path c’) [34–37] . In this case, the formation of a strong Me 3 Sn‐halogen bond [15] has a key role as the driving force of the process.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Visible Light Catalyzed Stannylation of Aryl Halides

Qiu,

Ren,

Yue

et al. 2024

Adv Synth Catal

View full text Add to dashboard Cite

A visible light‐mediated strategy for the preparation of aromatic stannanes from aryl halides (mostly aryl bromides) is presented herein. The reaction proceeds under metal‐ and additive‐free conditions and exhibits a broad substrate scope. The products obtained have been employed in the C‐C bond formation via Stille cross‐coupling reactions. Mechanistic investigation evidenced the key role of both aryl radical and trimethylstannyl radical in Ar‐Sn bond formation.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Visible Light Catalyzed Stannylation of Aryl Halides

Qiu,

Ren,

Yue

et al. 2024

Adv Synth Catal

View full text Add to dashboard Cite

show abstract

“…N ‐isopentylcrinasiaine ( 3Sa ) and anhydrolycorinone ( 3Sb ) followed by hippadine ( 3′Sb ) were both produced using the technique, with yields of 68 % and 88 %, respectively (Figure 28, Table 1S). [49] …”

Section: Examplesmentioning

confidence: 99%

Generation and Application of Aryl Radicals Under Photoinduced Conditions

Das,

Justin Thomas

2024

Chemistry A European J

View full text Add to dashboard Cite

Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon‐carbon and carbon‐heteroatom bonds. The synthetic applications of photoinduced aryl radical formation in the synthesis of complex organic compounds, including natural products, physiologically significant molecules, and functional materials, have received immense attention. An overview of current developments in photoinduced aryl radical production methods and their uses in organic synthesis is given in this article. A generalized idea of how to choose the reagents and approach for the generation of aryl radicals is described, along with photoinduced techniques and associated mechanistic insights. Overall, this article offers a critical assessment of the mechanistic results as well as the selection of reaction parameters for specific reagents in the context of radical cascades, cross‐coupling reactions, aryl radical functionalization, and selective C‐H functionalization of aryl substrates.

show abstract

“…In 2023, Baidya's group [15] developed an intramolecular cyclization method (Scheme 4) that exploits XAT processes to access phenanthridinone heterocyclic skeletons found in bioactive natural products [16] . The method transforms a wide array of iodo‐substituted N ‐aryl benzamides ( 7 ) into their corresponding phenanthridinone alkaloids ( 8 ) in good to excellent yields.…”

Section: C(sp2)–c(sp2) Bond Formationmentioning

confidence: 99%

An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

2023

View full text Add to dashboard Cite

The merging of photocatalysis with halogen‐atom transfer (XAT) processes has proven to be a versatile tool for the generation of carbon‐centered radicals in organic synthesis. XAT processes are unique in that they generate radicals without requiring the use of strong reductants necessary for the traditional single electron transfer (SET) activation of halides. Pathways to achieve XAT in synthetic applications can be categorized into three major sections: i) heteroatom‐based activators, ii) metal‐based activators, and iii) carbon‐based activators among which α‐aminoalkyl radicals have taken the center stage. Access to these α‐aminoalkyl radicals as XAT reagents has gained significant attention in the past few years due to the robustness of the reactions, the simplicity of the reagents required, and the broadness of their applications. Generation of these α‐aminoalkyl radicals is simply achieved through the single electron oxidation of tertiary amines, which after deprotonation at the α‐position generates the α‐aminoalkyl radicals. Due to the wide scope of tertiary amines available and the tunable nucleophilicity of α‐aminoalkyl radical formed, this strategy has become an attractive alternative to heteroatom/metal‐based radicals for XAT. In this minireview, we focus our attention on recent (2020‐2023) developments and uses of this robust technology to mediate XAT processes.

show abstract

A Visible-Light-Induced α-Aminoalkyl-Radical-Mediated Halogen-Atom Transfer Process: Modular Synthesis of Phenanthridinone Alkaloids

Cited by 12 publications

References 48 publications

Visible Light Catalyzed Stannylation of Aryl Halides

Visible Light Catalyzed Stannylation of Aryl Halides

Generation and Application of Aryl Radicals Under Photoinduced Conditions

An Overview of α‐Aminoalkyl Radical Mediated Halogen‐Atom Transfer

Contact Info

Product

Resources

About