Hypervalent Iodine Oxidation of Trimethylsilyl Ketene Acetals: A Convenient Route to α-Methoxylation of Esters and Lactones

Moriarty, Robert M.; Rani, Neena; Condeiu, C.; Duncan, Michael P.; Prakash, Om

doi:10.1080/00397919708004187

Cited by 31 publications

(11 citation statements)

References 17 publications

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“…In 1997, Moriarty, Prakash, and co‐workers reported the α‐methoxylation of trimethylsilyl ketene acetals by using iodosobenzene in dry methanol . Interestingly, the activation of iodosobenzene with a Lewis acid was not necessary in this methodology (Scheme ).…”

Section: Enol Substratesmentioning

confidence: 99%

Enol and Ynol Surrogates: Promising Substrates for Hypervalent Iodine Chemistry

Lauriers

Legault

2016

Asian J Org Chem

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This reviewisd edicated to Prof. Jean Lessard on the occasion of his 80th birthday Asian Abstract: In numerous iodine(III)-mediated methodologies that involve ketone compounds, the enol tautomer is expected to be the reactive species. In this context,t he exploration of enol and ynol surrogates as substrates is of great interest. Activated p-systems have been shown to exhibit interesting and highly exploitable behavior towardh ypervalent iodine reagents. This has led to the development of nu-merousu seful oxidativet ransformations. Enamines, enamides, enol derivatives, haloalkenes, and haloalkynes are all enol or ynol surrogates that are reactivet owards the most populari odanes and iodonium salts. This Focus Review will describep ast and on-going research involving these substrates to gain insighti nto the similarities and disparities observed in their reactivity profiles.The ORCID identification number(s) for the author(s) of this articlecan be found under http://dx.Scheme4.Proposed mechanism to explain 2 H-arizine formation and acetoxylation.Scheme5.Synthesis of 2-trifluoromethyloxazoles developed by Du, Zhao, and co-workers.Scheme6.Dichlorination of enaminesd evelopedbyZ hao, Du, and co-workers.Scheme7.Optimizedreductive conditionst oconvertthe dihaloimines to their corresponding enamines.

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Section: Enol Substratesmentioning

confidence: 99%

Enol and Ynol Surrogates: Promising Substrates for Hypervalent Iodine Chemistry

Lauriers

Legault

2016

Asian J Org Chem

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“…For example, fiveor six-membered lactams 19 could be obtained in moderate yields through the oxidation of cyclic amines 18 with PhIO using H 2 O as solvent ( Figure 5). 25 Moriarty et al 26 reported the oxidation of trimethylsilyl ketene acetals of lactones 20 in methanol, mediated by PhIO, to afford the corresponding α-methoxylated carbonyl compounds 21 in good yields ( Figure 6). They also found that reaction of dihydropyran 22 with PhIO in H 2 O could afford tetrahydro-2-furaldehyde 23 via carbocationic ring contraction ( Figure 7).…”

Section: Iodosylarenesmentioning

confidence: 99%

Hypervalent iodine reagents for heterocycle synthesis and functionalization

Sun¹,

Zhang‐Negrerie²,

Du³

et al. 2016

ROC

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Hypervalent iodine reagents have been vastly applied in many significant oxidative reactions. This surging interest in iodine reagents is mainly due to the very useful oxidizing properties, combined with their benign environmental character and commercial availability. In this review, we focus on the representative transformations that used the common hypervalent iodine reagents as oxidants in heterocycle synthesis and functionalizations, based on the type of the hypervalent iodine reagents.

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“…In past decades, different approaches have been provided to overcome the low solubility of PhIO in most organic solvents and water. Protonation of iodosylbenzene or treatment with a Lewis acid can be employed to depolymerize (PhIO)n …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization and Reactivity of Iodosylbenzene Nanoparticles as a New Nano–reagent

Zakavi

motlagh

2016

ChemistrySelect

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Iodosylbenzene (PhIO) and its derivatives are efficient terminal oxidants that have gained considerable attention. However, it suffers from limited solubility in most organic solvents and water. In the present study, the nanoparticles of iodosylbenzene has been synthesized with the aim of enhancing solubility in different solvents and its reactivity in oxidation reactions without any change in its chemical composition. Controlled alkaline hydrolysis of iodobenzene diacetate in the presence of (triethyleneglycol)monomethyl ether as stabilizer produced the nanoparticles. The average radius of the nanostructures determined by dynamic light scattering (DLS) and atomic force microscopy (AFM), was 149 and 71 nm, respectively. Also, the maximum height of nanoparticles measured from AFM images was 16 nm. Furthermore, scanning electron microscopy‐energy dispersive X‐ray analysis (SEM‐EDX) confirmed the formation of non‐spherical iodosylbenzene nanoparticles. The results of 1H and 13C NMR studies in DMSO‐d6 are in accord with the existence of different oligomeric iodosylbenzene particles in solution. This observation was also confirmed by the superimposed FT‐IR spectra of the bulk and nano‐sized products. Non‐catalytic oxidation of 1,5‐naphthalenediol to juglone with the bulk and nano‐sized oxidants, also the oxidation of styrene in the absence and presence of meso‐tetraphenylporphyrinatomanganese(III) acetate, confirmed the increased oxidizing ability of the nano‐sized oxidant.

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Hypervalent Iodine Oxidation of Trimethylsilyl Ketene Acetals: A Convenient Route to α-Methoxylation of Esters and Lactones

Cited by 31 publications

References 17 publications

Enol and Ynol Surrogates: Promising Substrates for Hypervalent Iodine Chemistry

Enol and Ynol Surrogates: Promising Substrates for Hypervalent Iodine Chemistry

Hypervalent iodine reagents for heterocycle synthesis and functionalization

Synthesis, Characterization and Reactivity of Iodosylbenzene Nanoparticles as a New Nano–reagent

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