Organic Polyvalent Iodine Compounds

Banks, David F.

doi:10.1021/cr60241a001

Cited by 230 publications

(77 citation statements)

References 94 publications

(117 reference statements)

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“…[1][2][3][4][5][6][7] In particular, both iodine(III) and iodine(V) compounds of the IL 3 and IL 5 types in which L is a monovalent electronegative ligand (i.e., λ 3 -iodanes and λ 5 -iodanes) can advantageously replace heavy metal-based reagents as inexpensive, non-toxic and yet efficient oxidants. The λ 3 -iodanes most commonly used today in oxidation reactions, including oxygenation reactions such as acetoxylation, methoxylation, hydroxylation, tosyloxylation and epoxidation, are (diacetoxyiodo)benzene (DIB), [bis(trifluoroacetoxy)iodo]benzene (BTI), [hydroxy(tosyloxy)iodo]benzene (HTI or "Koser's reagent") 8 and iodosylbenzene (PhIO, IOB).…”

Section: Introductionmentioning

confidence: 99%

Iodane-mediated and electrochemical oxidative transformations of 2-methoxy- and 2-methylphenols

Quideau¹,

Pouységu²,

Deffieux³

et al. 2003

Arkivoc

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A series of 2-methoxy and 2-methylphenols have been submitted to oxygenative oxidation reactions using (1) the λ 3 -iodane DIB, (2) a non-explosive and non-moisture sensitive version of the λ 5 -iodane IBX, named SIBX for Stabilized IBX, and (3) anodic oxidation with the aim of identifying the best reaction conditions for preparing orthoquinonoid cyclohexadienone synthons. Both the use of DIB and anodic oxidation appeared equally valuable for making orthoquinone dimethyl ketals, but the λ 3 -and λ 5-iodane reagents are more appropriate to induce ortho-oxygenation of 2-methylphenols. In particular, SIBX emerged as a useful reagent for mediating ortho-hydroxylation into dimerizing orthoquinols, a tactic that can be applied to the synthesis of natural bis(monoterpenoids) such as aquaticol.

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Section: Introductionmentioning

confidence: 99%

Iodane-mediated and electrochemical oxidative transformations of 2-methoxy- and 2-methylphenols

Quideau¹,

Pouységu²,

Deffieux³

et al. 2003

Arkivoc

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“…The known capability of iodonium compounds to undergo radical reaction (1)(2)(3)(4), the fact that most of the known enzymes to be severely inhibited, such as neutrophil NADH oxidase (5,6), cytochrome P-450 reductase (7), xanthine oxidase (8), nitric-oxide synthase (9), and sulfite reductase (10), involve radical chemistry in their mechanisms has led to the concept that inhibition by iodonium compounds is a marker of flavoprotein enzymes functioning by radical mechanisms, particularly because other flavoproteins, such as D-and L-amino acid oxidases, glucose oxidase, and glutathione reductase, which do not involve radicals in their reaction, are not inhibited (8). Previous work has demonstrated that the enzyme flavin needs to be reduced for inhibition to occur, and that the reaction of the reduced flavin with iodonium compounds results in phenyl adducts of the flavin (8,10).…”

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confidence: 99%

Reaction of Reduced Flavins and Flavoproteins with Diphenyliodonium Chloride

Chakraborty

Massey²

2002

Journal of Biological Chemistry

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The reaction of diphenyliodonium chloride with free reduced flavins has been studied by stopped flow spectrophotometry under anaerobic conditions, and second order rate constants were determined as a function of pH. The reactive flavin species was identified as the reduced anion, based on an observed reaction pK of 6.7. The product mixture was independent of the initial concentration of reactant and contained ϳ20% oxidized flavin. The results can be modeled quantitatively on a modification of the mechanism proposed by Tew (Tew, D. G. (1993) Biochemistry 32, 10209 -10215). The composition of the complex reaction mixture has been analyzed, and four flavin-phenyl adducts with distinctive absorbance and fluorescence characteristics have been identified, involving substitution at the flavin C4a, N5, and C8 positions. Inactivation of flavoprotein enzymes by diphenyliodonium has also been studied, and several examples were found where inactivation occurs readily, despite noninvolvement of radical intermediates in their reaction mechanisms. It can be concluded that inactivation by phenyliodonium species is not a valid indicator of catalytic mechanism involving radical intermediates. One of the several factors determining inactivation is maintenance of the enzyme flavin in the reduced form in the steady state of catalysis, the other factors being redox potential and accessibility of the inhibitor to the flavin active site.

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“…38,39) Moreover, phenyliodine(III) bis(trifluoroacetate) (PIFA) was chosen as the oxidative reagent for the phenol coupling based on reports that in addition to the coupling product only volatile products, i.e., iodobenzene and trifluoroacetic acid, remained after the PIFA-induced reaction. [33][34][35][36][37][43][44][45][46][47][48][49] At an initial stage of pretesting, we focused on the PIFAinduced phenol coupling of tri-O-methylated derivatives (7a, b) of pyrogallol-type norbelladine (6) to synthesize key intermediates 8a and 8b, and began with the preparation of 7a and 7b. 3,4,5-Trimethoxybenzaldehyde (9) was treated with tyramine in the presence of sodium borohydride to afford 10, which was derived to trifluoroacetamide 7a and formamide 7b.…”

Section: Resultsmentioning

confidence: 99%

Biomimetic Synthesis of (.+-.)-Galanthamine and Asymmetric Synthesis of (-)-Galanthamine Using Remote Asymmetric Induction

Node

Kodama

Hamashima

et al. 2006

CHEMICAL & PHARMACEUTICAL BULLETIN

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(؎)-Galanthamine (1) was synthesized in excellent yield by applying PIFA-mediated oxidative phenol coupling of N-(4-hydroxy)phenethyl-N-(3,4,5-trialkoxy)benzyl formamide (15b) as a key step. Because of the symmetrical characteristics of the pyrogallol moiety in the substrate (15b), the phenol coupling resulted in a sole coupling product except for volatile components from the oxidizing agent. On the basis of the successful results of the above strategy, (؊)-galanthamine (1) was synthesized by employing a novel remote asymmetric induction, where conformation of the seven-membered ring in the product of the phenol coupling was restricted by forming a fused-chiral imidazolidinone ring with D-phenylalanine on the benzylic C-N bond of the tri-O-alkylated gallyl amino moiety. The conformational restriction and successive debenzylation of the protected hydroxyl groups on the pyrogallol ring caused diastereoselective cyclization to yield a cyclic ether having the desired stereochemistry for the synthesis of (؊)-1.

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Organic Polyvalent Iodine Compounds

Cited by 230 publications

References 94 publications

Iodane-mediated and electrochemical oxidative transformations of 2-methoxy- and 2-methylphenols

Iodane-mediated and electrochemical oxidative transformations of 2-methoxy- and 2-methylphenols

Reaction of Reduced Flavins and Flavoproteins with Diphenyliodonium Chloride

Biomimetic Synthesis of (.+-.)-Galanthamine and Asymmetric Synthesis of (-)-Galanthamine Using Remote Asymmetric Induction

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