Visible-Light-Photocatalyzed Dicarbofunctionalization of Conjugated Alkenes with Ketone-Based Dihydroquinazolinones

Mondal, Pinku Prasad; Das, Subham; Venugopalan, Sreelakshmi; Krishnan, Malavika; Sahoo, Basudev

doi:10.1021/acs.orglett.3c00175

Cited by 17 publications

(2 citation statements)

References 52 publications

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“…Sahoo and co-workers further ventured into the construction of amides with α-stereogenic centers 55 from N -(arylsulfonyl) acrylamides 54 via visible-light photoredox-catalyzed alkyl radical addition/aryl migration/SO 2 extrusion cascade (Scheme 20 ). 33 In this strategy, [Ru(bpy) 3 (PF 6 ) 2 ] as photocatalyst, trace oxygen as oxidant, and blue LEDs as a light source was utilized. The generality of the alkyl radicals transferrable from DHQZs is similar to their previous report, encompassing mostly benzyl, secondary, and tertiary alkyl groups.…”

Section: Photochemical Reactions Of Ketone-derived Pro-aromatic Reagentsmentioning

confidence: 99%

Ketone-Derived Pro-aromatic Reagents for Radical Group Transfer Reactions and Deconstructive Functionalizations

Librando,

Liao,

Miñoza

2023

Synlett

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The recent prominence of ketones as handles for sp3-rich radicals has expanded the paradigm of synthetic utility of ketones, putting the ubiquitous functional group once again into the spotlight in recent years. One emerging strategy arose through ketone-derived pro-aromatic reagents in the form of dihydrobenzothiazoline (BTZ), dihydroquinazolinone (DHQZ), dihydropyrazole (DHP), and dihydro-1,2,4-triazole (DHT) as key intermediates for aromaticity-promoted C-C bond homolytic fission. The formed sp3-radicals could then participate in various radical functionalizations, including alkylations, arylations, olefination, alkynylation, silylations, amination, thiolation, and deuteration, among others, either in photocatalytic, thermal, or oxidative conditions. In this review, we highlight the implications and recent advances in using these pro-aromatic reagents in radical group transfer reactions and deconstructive functionalization. 1. Introduction 2. Aromatization-driven C-C bond scission for ketones 3. Photochemical reactions of ketone-derived pro-aromatic reagents 4. Non-photochemical reactions of ketone-derived pro-aromatic reagents 5. Conclusion and Future Outlook

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Section: Photochemical Reactions Of Ketone-derived Pro-aromatic Reagentsmentioning

confidence: 99%

Ketone-Derived Pro-aromatic Reagents for Radical Group Transfer Reactions and Deconstructive Functionalizations

Librando,

Liao,

Miñoza

2023

Synlett

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“…Among these, DHQZ is the widely employed pro‐aromatic motif. Research groups led by Zhu, [13] Martin, [14c–e] Sahoo, [14f–h] and our own [14b] have significantly advanced the use of ketone‐derived pro‐aromatic DHQZs, which have played an essential role in delivering alkyl radicals for diverse transformations, including amination, [14c] trifluoromethylation, [14e] alkylation, [14j] and arylation, [14d] among others [14] . Notably, DHQZ is also recognized as a privileged scaffold in medicinal chemistry even before its use as a group transfer reagent.…”

Section: Introductionmentioning

confidence: 99%

Pro‐aromatic Dihydroquinazolinones – From Multigram Synthesis to Reagents for Gram‐scale Metallaphotoredox Reactions

Tsai,

Li,

Paculba

et al. 2024

Chemistry An Asian Journal

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Dihydroquinazolinone (DHQZ) has recently been harnessed as a ketone‐derived pro‐aromatic reagent extensively employed in (metalla)photoredox reactions as versatile group transfer agents. In this work, we outline a column chromatography‐free protocol for the multigram‐scale synthesis of pro‐aromatic DHQZs as well as its use in a gram‐scale nickel/photoredox dual‐catalyzed cross‐coupling in single‐batch, photoflow, and simultaneous multiple smaller batches. While the single‐batch approach leveraged moderate yields, a simple plug‐flow photoreactor also exhibited amenable productivity (up to 45% yield) despite the use of a heterogeneous base. Meanwhile, performing the metallaphotoredox‐catalyzed reaction in multiple smaller batches in an improvised photoreactor facilitated high yields of up to 59% and good reproducibility, implying a convenient alternative in the absence of photoflow setups.

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Ruthenium‐Catalyzed Activation of Nonpolar C−C Bonds via π‐Coordination‐Enabled Aromatization

Shi

2023

Angewandte Chemie

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Activation of C−C bonds allows editing of molecular skeletons, but methods for selective activation of nonpolar C−C bonds in the absence of a chelation effect or a driving force derived from opening of a strained ring are scarce. Herein, we report a method for ruthenium‐catalyzed activation of nonpolar C−C bonds of pro‐aromatic compounds by means of π‐coordination‐enabled aromatization. This method was effective for cleavage of C−C(alkyl) and C−C(aryl) bonds and for ring‐opening of spirocyclic compounds, providing an array of benzene‐ring‐containing products. The isolation of a methyl ruthenium complex intermediate supports a mechanism involving ruthenium‐mediated C−C bond cleavage.

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Visible-Light-Photocatalyzed Dicarbofunctionalization of Conjugated Alkenes with Ketone-Based Dihydroquinazolinones

Cited by 17 publications

References 52 publications

Ketone-Derived Pro-aromatic Reagents for Radical Group Transfer Reactions and Deconstructive Functionalizations

Ketone-Derived Pro-aromatic Reagents for Radical Group Transfer Reactions and Deconstructive Functionalizations

Pro‐aromatic Dihydroquinazolinones – From Multigram Synthesis to Reagents for Gram‐scale Metallaphotoredox Reactions

Ruthenium‐Catalyzed Activation of Nonpolar C−C Bonds via π‐Coordination‐Enabled Aromatization

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