Photocatalyzed [2σ + 2σ] and [2σ + 2π] Cycloadditions for the Synthesis of Bicyclo[3.1.1]heptanes and 5- or 6-Membered Carbocycles

Nguyen, Tin V. T.; Bossonnet, André; Wodrich, Matthew D.; Waser, Jerome

doi:10.1021/jacs.3c09789

Cited by 78 publications

(24 citation statements)

References 74 publications

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“…With a relatively high strain energy (∼64 kcal mol −1 ), leveraging this thermodynamic driving force for cycloadditions has been a key aspect in this rapidly expanding field. 90–92 In this regard, our group discovered the first intermolecular [2π+2σ]-photocycloaddition mediated by energy transfer (Scheme 4B). 93 A series of commercially available endocyclic and aromatic double bonds, including coumarins, indoles, and flavones, were activated through energy transfer, readily undergoing cycloaddition with differently substituted bicyclo[1.1.0]butanes 29 .…”

Section: Recent Applications Of Triplet–triplet Energy Transfer In Or...mentioning

confidence: 99%

Energy transfer photocatalysis: exciting modes of reactivity

Dutta,

Erchinger,

Strieth-Kalthoff

et al. 2024

Chem. Soc. Rev.

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Section: Recent Applications Of Triplet–triplet Energy Transfer In Or...mentioning

confidence: 99%

Energy transfer photocatalysis: exciting modes of reactivity

Dutta,

Erchinger,

Strieth-Kalthoff

et al. 2024

Chem. Soc. Rev.

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“…For instance, Mykhailiuk and co-workers showed that 2-oxabicyclo[2.1.1]hexanes (oxa-BCHs), a potential bioisostere for meta -substituted arene rings, proved to be more hydrophilic and less lipophilic than proclaimed bicyclo[1.1.1]pentanes. , The oxa-BCH unit is further claimed to be 30 times more hydrophilic, less lipophilic, and more stable than the corresponding parent meta -substituted benzene ring. Since the conceptual advancement of “escape from flatland”, many reports from Brown, Studer, Procter, Molander, Leitch, Aggarwal, Li, Wang, Waser, Shi, Bach, and our group , displayed BCBs as potential precursors for 3D-chemical space exploration.…”

Section: Introductionmentioning

confidence: 99%

Double Strain-Release [2π+2σ]-Photocycloaddition

Dutta,

Lu,

Erchinger

et al. 2024

J. Am. Chem. Soc.

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In pursuit of potent pharmaceutical candidates and to further improve their chemical traits, small ring systems can serve as a potential starting point. Small ring units have the additional merit of loaded strain at their core, making them suitable reactants as they can capitalize on this intrinsic driving force. With the introduction of cyclobutenone as a strained precursor to ketene, the photocycloaddition with another strained unit, bicyclo[1.1.0]butane (BCB), enables the reactivity of both πunits in the transient ketene. This double strain-release driven [2π+2σ]-photocycloaddition promotes the synthesis of diverse heterobicyclo[2.1.1]hexane units, a pharmaceutically relevant bioisostere. The effective reactivity under catalyst-free conditions with a high functional group tolerance defines its synthetic utility. Experimental mechanistic studies and density functional theory (DFT) calculations suggest that the [2π+2σ]photocycloaddition takes place via a triplet mechanism.

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“…7 Bicyclobutane (BCB), the smallest fused strained hydrocarbon with a ring-strain of 64 kcal mol −1 , gained significant attention in recent years not only due to its unique structural features but also its ability to unlock strategies through strain release to synthetically challenging compounds either via single-electron or two-electron pathways. 8 For example, the stained carbon–carbon bond of BCB derivatives participates in various difunctionalization, 6 c ,9 carbene insertion, 10 or cycloaddition reactions, 11 leading to highly valuable carbocycles and heterocycles, which are bioisosteres of (hetero)arenes (Scheme 1B). 12 Despite the growing number of synthetic strategies using BCBs, reports on strain-enabled radical spirocyclization cascades haven't been studied to date.…”

Section: Introductionmentioning

confidence: 99%