Photocatalytic Aerobic Phosphatation of Alkenes

Depken, Christian; Krätzschmar, Felix; Rieger, Rene; Rode, Katharina; Breder, Alexander

doi:10.1002/anie.201711599

Cited by 47 publications

(29 citation statements)

References 68 publications

(53 reference statements)

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“…Considering the fact that the use of NFSI (2) as the terminal oxidant only led to moderate enantiomeric ratios, we turned our attention to a more generalized enantioselective selenocatalytic oxidation concept that-in the long run-potentially allowed for a broader scope of coupling partners to simple alkenes. Recently, our group disclosed a light-driven dual catalytic protocol that enabled for the first time the use of ambient air as the terminal oxidant in selenium-π-acid-catalyzed allylic alkene functionalizations [24][25][26][27][28]. A key asset of this strategy is the circumstance that various nucleophilic reaction partners, such as carboxylic acids, alcohols, and hydrogen phosphates, are compatible with aerobic conditions.…”

Section: Methodsmentioning

confidence: 99%

Rational Design of Chiral Selenium-π-Acid Catalysts

et al. 2019

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A series of unprecedented chiral selenium-π-acid catalysts for the asymmetric, oxidative functionalization of alkenes has been developed. In total, eleven different chiral dihydrodiselenocine and (di-)alkoxyphenyl (di)selenide motifs have been synthesized in a concise, modal, and straightforward fashion. Commercially available, non-racemic alcohols have been predominantly used as chiral building blocks for the facile assembly of the selenium-π-acid catalysts. These species have been exemplarily applied to the enantioselective intermolecular imidation and intramolecular acyloxylation of two olefins using N-fluorobenzenesulfonimide (NFSI) and ambient air, respectively, as terminal oxidants. In part, the catalysts provide very good yields of up to 99% and enantiomeric ratios of up to 83.5:16.5 under aerobic conditions.

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Section: Methodsmentioning

confidence: 99%

Rational Design of Chiral Selenium-π-Acid Catalysts

et al. 2019

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“…Although H 2 O 2 is known as a relatively clean oxidant due to generation no other waste than the water,,, it is on the other hand explosive and may become a dangerous reagent especially in large scale reactions. Therefore, new synthetic methods that can assemble the advantages of organoselenium catalysis and aerobic oxidation (using air or O 2 as the oxidant instead of H 2 O 2 ) are highly desirable in the field as this may resolve the remaining issues in Se‐catalyzed oxidation reactions ,,…”

Section: Methodsmentioning

confidence: 99%

Iron‐Enabled Utilization of Air as the Terminal Oxidant Leading to Aerobic Oxidative Deoximation by Organoselenium Catalysis

Chen

Cao

et al. 2018

Adv Synth Catal

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In contrast to conventional organoselenium-catalyzed oxidation reactions that require peroxide oxidants such as hydrogen peroxide, in this work we found that, addition of a low loading of iron (II) could enable the successful utilization of air as the terminal oxidant in organoseleniumcatalyzed oxidative deoximation reaction of ketoximes. This led to a new mild and relatively green aerobic oxidative deoximation method. Control reactions and X-ray photoelectron spectroscopy (XPS) analysis suggest that iron is crucial in the catalytic cycle, working to prohibit the deactivation of selenium catalyst through an iron-catalyzed aerobic oxidation of low valent selenium species by air to the active high valent selenium species. Since air can be utilized as the terminal oxidant, this work may contribute to the advance of organoselenium catalysis.

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“…The last transformation is particularly noteworthy, as it represents the first catalytic example of an allylic oxidative coupling of non‐activated hydrogen phosphates with simple alkenes 71 under aerobic conditions. The authors furthermore showed that the resulting allylic phosphates 79 could be directly converted with organocuprates to give the corresponding allylic alkylation products …”

Section: Redox Neutral and Oxidative C−c π‐Bond Functionalizationsmentioning

confidence: 99%

Light‐Driven Single‐Electron Transfer Processes as an Enabling Principle in Sulfur and Selenium Multicatalysis

Breder

Depken²

2019

Angew Chem Int Ed

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Cooperativity has become a mainstay in the context of multicatalytic reaction design. The combination of two or more catalysts that possess mechanistically distinct activation principles within a single chemical setting can enable bond constructions that would be impossible for any of the catalysts alone. An emerging subdomain within the field of multicatalysis is characterized by single‐electron transfer processes that are sustained by the synergistic merger of sulfur or selenium organocatalysis with photoredox catalysis. From a synthetic viewpoint, such processes have tremendous value, as they can offer new and economic pathways for the concise assembly of complex molecular architectures. Thus, the aim of this Review is to highlight recent methodological progress made in this area and to contextualize representative transformations with the mechanistic underpinnings that enable these reactions.

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Photocatalytic Aerobic Phosphatation of Alkenes

Cited by 47 publications

References 68 publications

Rational Design of Chiral Selenium-π-Acid Catalysts

Rational Design of Chiral Selenium-π-Acid Catalysts

Iron‐Enabled Utilization of Air as the Terminal Oxidant Leading to Aerobic Oxidative Deoximation by Organoselenium Catalysis

Light‐Driven Single‐Electron Transfer Processes as an Enabling Principle in Sulfur and Selenium Multicatalysis

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