Synthesis of Silyl Monoperoxyketals by Regioselective Cobalt-Catalyzed Peroxidation of Silyl Enol Ethers: Application to the Synthesis of 1,2-Dioxolanes

Hurlocker, Brisa; Miner, Matthew R.; Woerpel, K. A.

doi:10.1021/ol5020015

Cited by 32 publications

(23 citation statements)

References 36 publications

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“… 38 Treatment of these compounds with 5 mol % of SnCl 4 and alkene 29 , 30 , 38 , or 40 followed by immediate deprotection yielded FINO 2 ( 4 ) and derivatives 31 − 33 , 37 , 39 , and 41 . 38 …”

Section: Resultsmentioning

confidence: 99%

“…Treatment with LiN i Pr 2 yielded silyl enol ethers 23 − 25 and 35 . 38 Regioselective cobalt-catalyzed peroxidation of these products furnished mixed peroxyketals 26 − 28 and 36 . 38 Treatment of these compounds with 5 mol % of SnCl 4 and alkene 29 , 30 , 38 , or 40 followed by immediate deprotection yielded FINO 2 ( 4 ) and derivatives 31 − 33 , 37 , 39 , and 41 .…”

Section: Resultsmentioning

confidence: 99%

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FINO2 initiates ferroptosis through GPX4 inactivation and iron oxidation

et al. 2018

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Ferroptosis is a non-apoptotic form of regulated cell death caused by the failure of the glutathione-dependent lipid-peroxide-scavenging network. FINO2 is an endoperoxide-containing 1,2-dioxolane that can initiate ferroptosis selectively in engineered cancer cells. We investigated the mechanism and structural features necessary for ferroptosis initiation by FINO2. We found that FINO2 requires both an endoperoxide moiety and a nearby hydroxyl head group to initiate ferroptosis. In contrast to previously described ferroptosis inducers, FINO2 does not inhibit system xc− or directly target GPX4, as do erastin and RSL3, respectively, or deplete GPX4 protein, as does FIN56. Instead, FINO2 causes both indirect loss of GPX4 enzymatic function and directly oxidizes iron, ultimately causing widespread lipid peroxidation. These findings suggest that endoperoxides such as FINO2 can initiate a multi-pronged mechanism of ferroptosis.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

FINO2 initiates ferroptosis through GPX4 inactivation and iron oxidation

et al. 2018

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“…144 For example, hydrosilylperoxidation of silyl enol ether 18 gives peroxy compound 19 , and treatment of 19 with catalytic SnCl 4 at −78 °C in the presence of an alkene provides 1,2-dioxolane 20. Woerpel has also made 1,2-dioxepane rings.…”

Section: C-o Bondsmentioning

confidence: 99%

Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins

et al. 2016

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Cofactor-mimetic aerobic oxidation has conceptually merged with catalysis of syngas reactions to form a wide range of Markovnikov-selective olefin radical hydrofunctionalizations. We cover the development of the field and review contributions to reaction invention, mechanism and application to complex molecule synthesis. We also provide a mechanistic framework for understanding this compendium of radical reactions.

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“…Woerpel et al expanded the scope of this reaction to include silyl enol ethers. 23 Initial studies indicated that peroxidation of triethylsilyl enols ethers, rather than the more labile trimethyl silyl equivalents, resulted in fewer decomposition products, easier purication and higher yields. Further optimisation revealed that a combination of Co(thd) 2 in triuorotoluene led to an additional increase in yield.…”

Section: Isayama-mukaiyama Reactionmentioning

confidence: 99%

Advances in the synthesis of acyclic peroxides

et al. 2017

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Peroxide-containing compounds are an attractive synthetic target, given their widespread abundance in nature, with many displaying potent antimalarial and antimicrobial properties. This review summarises the many developments in the synthesis of acyclic peroxides, with a particular focus on the past 20 years, and seeks to update organic chemists about these new approaches. The synthetic methodologies have been subdivided into metal-catalysed reactions, organocatalytic reactions, direct oxidation reactions, miscellaneous reactions and enzymatic routes to acyclic peroxides

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Synthesis of Silyl Monoperoxyketals by Regioselective Cobalt-Catalyzed Peroxidation of Silyl Enol Ethers: Application to the Synthesis of 1,2-Dioxolanes

Abstract: The cobalt-catalyzed peroxidation of silyl enol ethers with molecular oxygen and triethylsilane provided silyl monoperoxyketals in 54%-96% yield. These compounds serve as precursors to peroxycarbenium ions, which undergo annulations to provide 1,2-dioxolanes.

Cited by 32 publications

References 36 publications

FINO2 initiates ferroptosis through GPX4 inactivation and iron oxidation

FINO2 initiates ferroptosis through GPX4 inactivation and iron oxidation

Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins

Advances in the synthesis of acyclic peroxides

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