Addition of aldehydes to unsaturated compounds induced by autooxidation

Vinogradov, M. G.; Kereselidze, R. V.; Gachechiladze, G. G.; Nikishin, G. I.

doi:10.1007/bf00905535

Cited by 7 publications

(2 citation statements)

References 2 publications

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“…On the commodity scale, autoxidation of cumene and p-xylene produce phenol 5 and terephthalic acid, 6 respectively (Figure 1B). In fine-chemical synthesis, acyl radical intermediates generated during aldehyde autoxidation (Figure 2A) have been diverted toward olefin addition chemistry (Figure 2B), 7,8 alkyl radical intermediates generated by decarbonylation of acyl radicals have been harnessed for alkylation of N-heterocycles (Figure 2C), 9 and peroxy radicals and peroxide intermediates have been diverted toward oxygen-atom transfer (OAT) chemistry to olefins (i.e., Mukaiyama reaction) [10][11][12] and to transition-metal complexes (Figures 2D and 2E). [13][14][15] Although these examples highlight the potential of autoxidation in specific synthetic applications, reliance on only those reactive intermediates generated in autoxidation chemistry substantially limits the diversity of substrate functionalization reactions that can be coupled to O 2 .…”

Section: Introductionmentioning

confidence: 99%

The Role of Iodanyl Radicals as Critical Chain Carriers in Aerobic Hypervalent Iodine Chemistry

Hyun

Yuan

Maity

et al. 2019

Chem

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Aerobic hypervalent iodine chemistry provides a strategy for coupling the oneelectron chemistry of O 2 with two-electron processes typical of organic synthesis. We show that in contrast to the canonical two-electron oxidation of aryl iodides, aerobic synthesis proceeds by a radical chain process initiated by the addition of aerobically generated acetoxy radicals to aryliodides to generate iodanyl radicals. Robustness analysis reveals that the developed aerobic oxidation chemistry displays substrate tolerance similar to that observed in peracid-based methods and thus holds promise as a sustainable synthetic method.

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Section: Introductionmentioning

confidence: 99%

The Role of Iodanyl Radicals as Critical Chain Carriers in Aerobic Hypervalent Iodine Chemistry

Hyun

Yuan

Maity

et al. 2019

Chem

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“…The reactive acyl radical intermediates, which are obtained from oxidative cleavage of aldehydes, form the basis of some industrial synthetic processes . The acyl radicals formation from the auto‐oxidation of aldehydes by transition‐metal ions was extensively reported, meanwhile the metal‐free aerobic auto‐oxidation of aldehydes is very interesting approach (Figure b) . Despite the importance of acyl radicals, which were produced from auto‐oxidation of aldehydes, there have been limited reports about their synthetic aspects and most existing reports investigate the hydroacylation reactions …”

Section: Introductionmentioning

confidence: 99%

Heteroaromatic Aldehydes with Unprecedented Catalytic Performance in Selective Radical Reactions: Synthesis of α‐Aminophosphonate Scaffolds

et al. 2019

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Heterocyclic compounds have gained immense importance because of their low resonance energy and strong hydrogen-bonding abilities, which provide good catalytic potential in a variety of organic transformations. Herein an unexpected metal-free catalytic performance of heteroaromatic aldehydes has been reported. Accordingly, a unique method for the synthesis of new scaffolds of peptidomimetic compounds, α-aminophosphonates has been developed, which was difficult using previous methods. The aerobic auto-oxidation of heteroaromatic aldehydes acts as a driving force for the coupling of aromatic N-benzylamines and hydrophosphoryl compounds according to a one-pot, metal-and solvent-free procedure. Heteroaromatic aldehydes, in addition to their individual ability to promote selective radical reactions through the auto-oxidation process, can provide hydrogen bonding frameworks at different stages of the reaction and thereby change the reaction pathways and induce new activities and selectivities, which unveiled their other important catalytic features. We believe that this highlights the catalytic potential of heteroaromatic aldehydes, which may offer an opportunity to change the traditional harsh conditions necessary to generate alkyl radicals.[a] Dr. reaction, as monitored by TLC, the reaction mixture was allowed to cool at room temperature. The mixture was then extracted with ethyl acetate three times and dried over MgSO 4 , filtered, and concentrated under reduced pressure. 4 5 6 7 8

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Direct Homolytic Oxidation by Metal Complexes

Sheldon¹

1981

Metal-Catalyzed Oxidations of Organic Compounds

117

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Addition of aldehydes to unsaturated compounds induced by autooxidation

Cited by 7 publications

References 2 publications

The Role of Iodanyl Radicals as Critical Chain Carriers in Aerobic Hypervalent Iodine Chemistry

The Role of Iodanyl Radicals as Critical Chain Carriers in Aerobic Hypervalent Iodine Chemistry

Heteroaromatic Aldehydes with Unprecedented Catalytic Performance in Selective Radical Reactions: Synthesis of α‐Aminophosphonate Scaffolds

Direct Homolytic Oxidation by Metal Complexes

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