Visible Light-Mediated Decarboxylation Rearrangement Cascade of ω-Aryl-<i>N</i>-(acyloxy)phthalimides

Faderl, Christian; Budde, Simon; Kachkovskyi, Georgiy; Rackl, Daniel; Reiser, Oliver

doi:10.1021/acs.joc.8b01538

Cited by 29 publications

(20 citation statements)

References 47 publications

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“…Authors propose a distinct energy-transfer mechanism leading to decarboxylative radical generation. 933 , 934 …”

Section: Reductive Transformations Of Carbonyls Imines and Other X=y Functional Groups Through Photochemical And Electrochemical Pcet Promentioning

confidence: 99%

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

et al. 2021

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We present here a review of the photochemical and electrochemical applications of multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms in which both an electron and a proton are exchanged together, often in a concerted elementary step. As such, MS-PCET can function as a non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from a wide variety of common organic functional groups. We present an introduction to MS-PCET and a practitioner’s guide to reaction design, with an emphasis on the unique energetic and selectivity features that are characteristic of this reaction class. We then present chapters on oxidative N–H, O–H, S–H, and C–H bond homolysis methods, for the generation of the corresponding neutral radical species. Then, chapters for reductive PCET activations involving carbonyl, imine, other X=Y π-systems, and heteroarenes, where neutral ketyl, α-amino, and heteroarene-derived radicals can be generated. Finally, we present chapters on the applications of MS-PCET in asymmetric catalysis and in materials and device applications. Within each chapter, we subdivide by the functional group undergoing homolysis, and thereafter by the type of transformation being promoted. Methods published prior to the end of December 2020 are presented.

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“…Authors propose a distinct energy-transfer mechanism leading to decarboxylative radical generation. 933 , 934 …”

Section: Reductive Transformations Of Carbonyls Imines and Other X=y Functional Groups Through Photochemical And Electrochemical Pcet Promentioning

confidence: 99%

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

et al. 2021

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“…The ipso attack is kinetically more feasible, affording a spiro intermediate III through a transition state TS2 ipso with a 13.41 kcal/mol barrier that is slightly lower than that for the ortho attack to afford IV ( TS2 ortho ; Δ G ⧧ = 15.33 kcal/mol). , Then, the single-electron oxidation of III on the anode affords cationic intermediate III + . Notably, carbonyl migration in III + is much more favorable kinetically through TS3 C (Δ G ⧧ = 3.01 kcal/mol) than iminyl migration ( TS3 N ; Δ G ⧧ = 13.22 kcal/mol) even though the energy of intermediate V is higher than that of IV + . Finally, the deprotonation of V affords quinazolinone 2a .…”

mentioning

confidence: 99%

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Hwang

Cho

2021

Org. Lett.

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Electrochemistry has recently emerged as a sustainable approach for efficiently generating radical intermediates utilizing eco-friendly electric energy. An electrochemical process was developed to transform 1,2,4-oxadiazolines under mild conditions. The electrochemical N−O bond cleavage at a controlled oxidation potential led to the selective synthesis of quinazolinone derivatives that could not be obtained by photocatalytic radical processes, indicating complementary reactivities in radical processes. The electrochemical reaction pathways were fully revealed by density functional theory-based investigations.

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“…The procedure also allowed for the retention of stereocentres on the ethyl linker, and was used for the synthesis of an N-protected precursor to the ADHD treatment amphetamine in high enantiomeric excess. [65] MeO O N Ir(dtbbpy)(ppy) Greaney and co-workers showed that the tandem use of decarboxylation and desulfonylation could be used in a Truce-Smiles rearrangement under mild conditions. [66] Firstly, benzophenone oxime ester 76 is photosensitized by the iridium catalyst, resulting in decarboxylation and generation of a reactive primary alkyl radical (Scheme 25).…”

Section: Smiles Rearrangementmentioning

confidence: 99%

“…The procedure also allowed for the retention of stereocenters on the ethyl linker and was used for the synthesis of an N-protected precursor to an ADHD treatment amphetamine with high enantiomeric excess. 65 Scheme 24 Decarboxylative Smiles rearrangement (Reiser group)…”

Section: Scheme 23 N-to-n Aryl Migration Reaction Via the Reduction Of Alkyl Azides (Yu Group)mentioning

confidence: 99%

Recent Advances in the Smiles Rearrangement: New Opportunities for Arylation

Whalley¹,

Greaney²

2021

Synthesis

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The Smiles rearrangement has undergone a renaissance in recent years providing new avenues for non-canonical arylation techniques in both the radical and polar regimes. This Short Review will discuss recent applications of the reaction (from 2017 onwards), including its relevance to areas such as heterocycle synthesis, functionalisation of alkenes and alkynes as well as glimpses at new directions for the field.

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Visible Light-Mediated Decarboxylation Rearrangement Cascade of ω-Aryl-N-(acyloxy)phthalimides

Cited by 29 publications

References 47 publications

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Complementary Reactivity in Selective Radical Processes: Electrochemistry of Oxadiazolines to Quinazolinones

Recent Advances in the Smiles Rearrangement: New Opportunities for Arylation

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