Phenyliodine Diacetate Research Articles

Hypervalent Iodine Mediated Synthesis of Thiosulfonates from Sulfonyl Hydrazides and Their Transformation into Symmetrical Disulfides

AbstractA transition-metal-free synthesis of thiosulfonates has been accomplished by the disproportionate coupling of readily available and inexpensive sulfonyl hydrazides embracing hypervalent iodine(III) [phenyliodine(III) diacetate (PIDA)] as an oxidant. This synthesis involves cleavage of the S–N bond and is endowed with creation of a new S–S bond. The thiosulfonates were further reduced with CS2/KOH to obtain symmetrical disulfides. This protocol features mild reaction conditions in open air, an inexpensive oxidant, and high functional group tolerance with good to excellent product yields.

Synthesis of polyurethanes through the oxidative decarboxylation of oxamic acids: a new gateway toward self-blown foams.

Polyurethane (PU) thermoplastics and thermosets were prepared through the step-growth polymerization of in situ generated polyisocyanates through the decarboxylation of polyoxamic acids, in the presence of phenyliodine diacetate (PIDA), and polyols. The CO2 produced during the reaction allowed the access to self-blown polyurethane foams through an endogenous chemical blowing. The acetic acid released from ligand exchange at the iodine center was also shown to accelerate the polymerization reaction, avoiding the recourse to an additional catalyst. Changing simple parameters during the production process allowed us to access flexible PU foams with a wide range of properties.

Organoiodine-mediated dehydrogenative N–N coupling of aryl alkoxycarbamates

An environmentally benign and efficient approach has been developed for the construction of corresponding N–N coupled dialkoxyhydrazines in good yields (up to 91%) via phenyliodine diacetate (PIDA) mediated oxidative dimerization of alkoxycarbamates. The advantages of this transformations are mild conditions, functional-group tolerance and operationally simple. Notably, the cross-coupling of two different aryl alkoxycarbamates is also demonstrated, which provides a straightforward method to structurally complex N–N molecules.

One-pot synthesis of N-acylated ureas using phenyliodine (III) diacetate (PIDA) as N-acylation agent

An effective method was explored for the one-pot synthesis of N-acylated urea derivatives by the reaction of substituted isothiocyanatobenzenes, primary amines and PIDA (phenyliodine (III) diacetate) in one-pot manner. Mild reaction conditions, short reaction time, high efficiency and readily accessible materials are the features of this method, making suitable and alternative for the preparation of a variety of biologically or pharmaceutically active compounds.

Oxidative Assemblies of Flavonoids Dimers – Synthesis of Dehydrodicatechin A

AbstractCatechin and quercetin were subjected to different oxidative conditions. Reagents such as silver oxide, potassium ferricyanide or PIDA (phenyliodine diacetate), as well as electrochemical and photocatalytic conditions were evaluated. From quercetin, the formation of a dimer resulting from an oxa‐Diels‐Alder has been systematically observed. From catechin, dehydrodicatechin A was obtained by the action of silver oxide in a toluene/acetone mixture. Complementary experiments in the presence of catechol gave information on the mechanisms of formation. Products resulting from these reactions have already been identified in plants and beverages made from plants and are supposed to result from the oxidation of flavonoids. This reactivity exploration provides a better understanding of the role of catechols in the formation of natural compounds arising from the dimerization of flavonoids during oxidative process. These results shed some light on the intrinsic reactivity of catechin and quercetin.

Applications of Phenyliodine(III)diacetate in C−H Functionalization and Hetero‐Hetero Bond Formations: A Septennial Update

AbstractOne of the most widely utilized hypervalent iodines used as an oxidizing agent in organic chemistry is (diacetoxyiodo)benzene (PhI(OAc)2), also known as (DAIB), phenyliodine(III) diacetate (PIDA). In this review, authors have comprehensively and systematically presented the various applications of PIDA in organic synthesis involving C−C, C‐hetero, hetero‐hetero and multiple bond forms from the summer of 2015 to the present. The role of PIDA was also emphasized for the success of particular organic transformation. Recent literature has produced a substantial number of publications (∼100), and this septennial review examines all of the most recent breakthroughs in the field of study.

Oxidation of a triple carbo[5]helicene with hypervalent iodine

Stereochemistry was found to be a critical factor in the reactivity of the diastereomers of the prototypical triple carbo[5]helicene hexabenzotriphenylene (HBTP): D3-HBTP could be converted into an oxidation rearranged product, but C2-HBTP could not be converted.

Synthesis of Unsymmetric Thiosulfonates Starting from N-Substituted O-Thiocarbamates: Easy Access to the S–SO2 Bond

Using phenyliodine diacetate as an oxidant and nickel acetate as a promoter, a wide range of unsymmetric thiosulfonates could be furnished easily in moderate to excellent yields starting from N-substituted O-thiocarbamates and sodium sulfinates. This protocol features mild conditions, short reaction times, and high atomic utilization, which can provide an alternative method for the synthesis of unsymmetric thiosulfonates. In addition, the reaction could be scaled up on a gram scale, showing potential application value in industry.

Phenyliodine(III) diacetate-induced regioselective synthesis of 1-(benzoxazol-2-yl)-1-alkoxynaphthalen-2(1H)-ones from 2-(2-hydroxynaphthyl)benzoxazoles

Phenyliodine(III) diacetate-induced oxidation of 2-(2-hydroxynaphthyl)benzoxazoles in alcohols, regioselectively afforded dearomatized products: 1-(benzoxazol-2-yl)-1-alkoxynaphthalen-2(1H)-ones and 1-(benzoxazol-2-yl)naphthalene-2,3-diones. Further, these products were also synthesized in one-pot either from (E)-1-(((2-hydroxyphenyl) imino)methyl)naphthalen-2-ol or 2-aminophenol and 2-hydroxynaphthaldehyde by varying the amount of phenyliodine(III) diacetate in different alcohols. The structure of these compounds was established on the basis of FTIR, NMR, and mass spectral data as well as X-ray crystallographic data.

Phenyliodine(III) diacetate-mediated dearomatization of 2-(2-hydroxyaryl)benzoxazoles and 2-(2-hydroxyaryl)benzothiazoles: Regio- and stereoselective synthesis of tetramethoxycyclohexenones and bicyclo[2.2.2]octenones

A range of stereochemically defined oxidative dearomatization products formed by treating 2-(2-hydroxyaryl)benzoxazoles and 2-(2-hydroxyaryl)benzothiazoles with phenyliodine(III) diacetate have been described, demonstrating remarkable regiochemical and stereochemical dictated by the nature of the phenol substituents. Benzoxazole-substituted phenols undergo dearomatization leading to the regio- and stereoselective synthesis of tetramethoxy-substituted cyclohexenones (4,4,5,6-tetramethoxycyclohex-2-en-1-ones). However, benzothiazole-substituted phenols readily undergo regio- and stereoselective [4+2] dimerization to bicyclo[2.2.2]octenone. Further, halogenated 2-(2-hydroxyaryl)benzoxazoles lead to formation of a different tetramethoxy-substituted cyclohexenones (2,4,5,6-tetramethoxycyclohex-2-en-1-ones) whereas halogenated 2-(2-hydroxyaryl)benzothiazoles afforded 4-methoxycyclohexa-2,5-dien-1-ones. The structure of all the compounds were established using NMR, FT-IR and HRMS techniques, and the structure of two compounds were confirmed by X-ray crystallography.

An Efficient and Practical Construction of S−N Bond from Aryl Thioureas and Amines under Metal‐Free Conditions

AbstractAn efficient and practical construction of S−N bond from aryl thioureas and amines under mild and metal‐free conditions is reported. A series of sulfenamides was obtained smoothly from aryl thioureas and amines (mainly secondary amines) through cross dehydrogenation coupling reaction (CDC) in the presence of phenyliodine(III) diacetate. The protocol features easily available starting materials, easy and odorless performance, mild reaction conditions, good yields, and a broad substrate scope, illustrating its synthetic value for the synthesis of diverse biologically or pharmaceutically relevant compounds.

Visible Light-Induced 4-Chromanones Synthesis: Radical Cascade Cyclization of α-Oxocarboxylic Acids with o-(Allyloxy)arylaldehydes Promoted by Phenyliodine(III) Diacetate

Visible Light-Induced 4-Chromanones Synthesis: Radical Cascade Cyclization of <i>α</i>-Oxocarboxylic Acids with <i>o</i>-(Allyloxy)arylaldehydes Promoted by Phenyliodine(III) Diacetate

Switchable synthesis of 1,4-bridged dihydroisoquinoline-3-ones and isoquinoline-1,3,4-triones through radical oxidation of isoquinolinium salts with phenyliodine(iii) diacetate

A switchable synthesis of 1,4-bridged dihydroisoquinoline-3-ones and isoquinoline-1,3,4-triones is developed via radical oxidation of isoquinolinium salts with PhI(OAc)2.

Oxidative β-Cleavage of Fused Cyclobutanols Leading to Hydrofuran-Fused Polycyclic Aromatic Compounds.

Treatment of aryl-fused bicyclo[4.2.0]octanols with an oxidant such as phenyliodine diacetate (PIDA) or hypochlorous acid gave dihydrofuran-containing polycyclic aromatic compounds by selective β-cleavage of the cyclobutanol moiety. Mechanistic studies suggest that the oxygen atom of the hydrofuran ring is incorporated from the hydroxy group of the substrate via intramolecular addition. The oxidative transformation should serve as a new method to prepare functionalized polycyclic aromatic compounds.

One‐Pot Synthesis of Diazirines and 15N2‐Diazirines from Ketones, Aldehydes and Derivatives: Development and Mechanistic Insight

AbstractBroad scope one‐pot diazirine synthesis strategies have been developed using two different oxidants depending on the nature of the starting material. In all cases, an inexpensive commercial solution of ammonia (NH3) in methanol (MeOH) was employed, avoiding the difficult use of liquid ammonia. With aliphatic ketones, t‐butyl hypochlorite (t‐BuOCl) was found to be the best oxidant whereas it is preferable to use phenyliodine diacetate (PIDA) with aromatic ketones, aldehydes and imines. The nature of the imine‐protecting group is essential and only t‐butyl imine allowed the synthesis of 15N2‐diazirine with complete 15N incorporation, emphasizing a key trans‐imination step in the reaction mechanism. These methods are operationally simple, and tolerant to most functional groups, providing diazirines with yields ranging from 20 to 99%.magnified image

Gold-Catalyzed Tandem Oxidative Coupling Reaction between β-Ketoallenes and Electron-Rich Arenes to 2-Furylmethylarenes.

A tandem oxidative coupling reaction of β-ketoallenes and arenes was developed, which leads to the formation of 2-furylmethylarenes using AuCl3 and phenyliodine diacetate. The AuIII salt catalyzed the cyclization of β-ketoallenes to form a 2-furylmethyl gold intermediate, and the subsequent C-H functionalization of arenes proceeded smoothly. During the oxidative coupling, nucleophilic additions occurred at the center and terminal carbon atoms of the allene moiety to form C-O and C-C bonds.

Computational study of phenyliodine diacetate intermediates during Lewis acid activation with TMSOTf

Computational study of phenyliodine diacetate intermediates during Lewis acid activation with TMSOTf

Oxidative ring expansion of 3-hydroxy-3-phenacyloxindoles using phenyliodine diacetate and molecular iodine: Synthesis of 2-hydroxy-2-aryl/alkyl-2,3-dihydroquinolin-4(1H)-ones

Oxidation of tertiary alcohol of the type 3-hydroxy-3-phenacyloxindoles using the combination of phenyliodine diacetate and molecular iodine in methanol results in oxidative cleavage of C2-C3 bond to form isocyanate as an intermediate with its subsequent trapping by methanol to form ortho-carbamates of 1,3-diaryl carbonyl compounds which further undergoes concurrent cyclization to furnish 2-hydroxy-2-aryl/alkyl-2,3-dihydroquinolin-4(1H)-ones derivatives in good yields.

Dienaminodiones, new push-pull alkenes, from 3,4-dihydroxysalicylaldehyde-derived Schiff base

An atom-economical one-pot synthesis of a new push-pull dienaminodiones from a 3,4-dihydroxysalicylaldehyde-derived Schiff base and indoles in the presence of phenyliodine(III) diacetate is described. Variation of indoles and anilines constitute a broad substrate scope of the methodology with good to moderate yields. Formation of Schiff base followed by an indole addition to afford dienaminodione takes place in one-pot; thus, the present method serves as a sequential multicomponent reaction. The present work also serves as a methodology to afford indole variants of natural product talaroenamine B.

Silver-Catalyzed Remote C5-H Selenylation of Indoles.

Remote C-H functionalization at C5 is the most sparingly observed selectivity in the functionalization of indole templates. Herein, we reported that the combination of a AgSbF6 catalyst and phenyliodine diacetate oxidation enabled the C-H selenylation at the C5 position of indole scaffolds in a selective version, thus leading to the formation of a wide scope of 5-selenylated indole derivatives, which are otherwise difficult to prepare. Mechanistic studies indicated that current transformation follows a radical process, and the tethered C3 pivaloyl group on indole scaffolds plays roles in both blocking the active C3 position and manipulating the electronic affinity of the arenes.