Asymmetric, visible light-mediated radical sulfinyl-Smiles rearrangement to access all-carbon quaternary stereocentres

Hervieu, Cédric; Kirillova, Mariia S.; Suárez, Tatiana; Müller, Marco; Merino, Estı́baliz; Nevado, Cristina

doi:10.1038/s41557-021-00668-4

Cited by 121 publications

(64 citation statements)

References 54 publications

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“…unactivated alkenes, Michael acceptors, styrenes, alkynes and vinyl ureas) is a highly versatile approach to secondary alkyl radicals, which can then undergo the key aryl transfer from an appropriately disposed sulfonamide 4 [2] . An innovative development in this area was recently reported by Nevado and co‐workers, who demonstrated stereoselective aryl transfer using chiral sulfinamides [2h] . However, the applicability of these systems is often constrained by structural limitations of the substrates and electronic compatibility of incoming radical coupling partners.…”

Section: Methodsmentioning

confidence: 99%

Truce–Smiles Rearrangements by Strain Release: Harnessing Primary Alkyl Radicals for Metal‐Free Arylation

2021

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The ring‐opening of 3‐aminocyclobutanone oximes enables easy generation of primary alkyl radicals, capable of undergoing an unprecedented strain‐release, desulfonylative radical Truce–Smiles rearrangement, providing divergent access to valuable 1,3 diamines and unnatural β‐amino acids. Characterized by mild conditions and wide scope of migrating species, this protocol allows the modular assembly of sp3‐aryls under transition metal‐free, room‐temperature conditions.

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Section: Methodsmentioning

confidence: 99%

Truce–Smiles Rearrangements by Strain Release: Harnessing Primary Alkyl Radicals for Metal‐Free Arylation

2021

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“…48 49 50 51 52 In 2021, they reported the first asymmetric variant of this rearrangement in the radical manifold, exploiting chiral sulfinamide substrates. 53 Using an iridium photocatalyst at room temperature, species such as sulfonyl chlorides and alkyl halides were reduced to open shell species, capable of undergoing intermolecular addition to sulfinamides such as 53 (Scheme 15 ). A Truce–Smiles rearrangement can then occur, yielding an all-carbon quaternary center with a transfer of chirality from the sulfinamide to the newly formed stereocenter 54 .…”

Section: Radical Smiles: Alkene and Alkyne Functionalizationmentioning

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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“…1a ) 63 – 65 . Very recently, the same group published a stereoselective variant of this reaction in which enantiomerically pure acrylamides were used as starting materials that contain a chiral aryl sulfinyl group as a stereodirecting moiety which also serves as the aryl donor 66 . Along with radical addition to acrylates, such α-amide radical intermediates can also be generated via reductive C−X-bond cleavage of α-halo(sulfon)amides 67 or via intramolecular hydrogen atom transfer to aryl radicals by using ortho -iodoaryl sulfonamides as radical precursors 68 .…”

Section: Introductionmentioning

confidence: 99%

1,4-Aryl migration in ketene-derived enolates by a polar-radical-crossover cascade

Radhoff

Studer

2022

Nat Commun

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The arylation of carboxylic acid derivatives via Smiles rearrangement has gained great interest in recent years. Both radical and ionic approaches, as well as radical-polar crossover concepts, have been developed. In contrast, a reversed polar-radical crossover approach remains underexplored. Here we report a simple, efficient and scalable method for the preparation of sterically hindered and valuable α-quaternary amides via a polar-radical crossover-enolate oxidation-aryl migration pathway. A variety of easily accessible N-alkyl and N-arylsulfonamides are reacted with disubstituted ketenes to give the corresponding amide enolates, which undergo upon single electron transfer oxidation, a 1,4-aryl migration, desulfonylation, hydrogen atom transfer cascade to provide α-quaternary amides in good to excellent yields. Various mono- and di-substituted heteroatom-containing and polycyclic arenes engage in the aryl migration reaction. Functional group tolerance is excellent and substrates as well as reagents are readily available rendering the method broadly applicable.

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Asymmetric, visible light-mediated radical sulfinyl-Smiles rearrangement to access all-carbon quaternary stereocentres

Cited by 121 publications

References 54 publications

Truce–Smiles Rearrangements by Strain Release: Harnessing Primary Alkyl Radicals for Metal‐Free Arylation

Truce–Smiles Rearrangements by Strain Release: Harnessing Primary Alkyl Radicals for Metal‐Free Arylation

Recent Advances in the Smiles Rearrangement: New Opportunities for Arylation

1,4-Aryl migration in ketene-derived enolates by a polar-radical-crossover cascade

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