Thottumkara, 1178 stacy lane, macomb, il 61455 macomb high school, macomb, il teacher and or mentor. Synthesis and oxidation reactions of a user and eco. Hypervalent iodine mediated paraselective fluorination of. A modified procedure for the direct synthesis of hypervalent bistrifluoroacetoxyiodoarenes avoids the use of hazardous reagents with the workup being only an aqueous extraction. The final chapter provides an overview of the important practical applications of polyvalent iodine compounds in medicine and industry. Iodoxolonebased hypervalent iodine reagents organic letters. The obtained acetylenes are important building blocks for organic chemistry, material sciences and chemical biology. Hypervalent iodinehf reagents for the synthesis of 3fluoropyrrolidines tsugio kitamura, azusa miyake, kensuke muta, and and juzo oyamada department of chemistry and applied chemistry, graduate school of science and engineering, saga university, honjomachi, saga 8408502, japan. Hypervalent iodine reagents for heterocycle synthesis and. Iii and iodine v oxidants, recyclable monomeric hypervalent iodine iii reagents, reactions of hypervalent iodine in solid state, application of water or recyclable organic solvents in these reactions, and catalytic systems based on hypervalent. Program in chemistry, the graduate center of the city university of new york. Reactions of hypervalent iodine reagents in green solvents and under.
Hypervalent iodinev reagents, such as 2iodoxybenzoic acid ibx and dessmartin periodinane dmp, have found widespread synthetic application as stoichiometric oxidants for the facile and selective oxidation of alcohols to respective. For example, iiii reagents have been used in place of aryl halides for diverse pdcatalyzed c. The anodic oxidation of aryl iodides is a powerful method for the synthesis of hypervalent iodine reagents, which eliminates the necessity to use expensive or hazardous chemical oxidizing reagents. New insights have led to many research activities during the last years, which are clearly reflected in the many high quality contributions assembled in this series. The fast access to simple z 3iodo acrylic acid derivatives which can be easily oxidized to the corresponding hypervalent iodine iii reagents is described. The fast access to simple z3iodo acrylic acid derivatives which can be easily oxidized to the corresponding hypervalent iodine iii reagents is described.
Although the ritter reaction is a reliable approach for preparing. In combination with recyclable and reusable hypervalent iodine reactions, ruthenium catalysts could be used as a green and efficient catalytic oxidative system, for oxidation of alcohols and sulfides in water. Hypervalent iodine iii derivatives have been established as powerful reagents in organic transformations, but so far only few studies have addressed their use as halogenbonding noncovalent lewis acids. Preparation, structure, and synthetic applications of polyvalent iodine compounds kindle edition by zhdankin, viktor v download it once and read it on your kindle device, pc, phones or tablets. In summary, we have synthesized an user and eco friendly hypervalent iodine reagent capable of selectively oxidizing allylic and benzylic alcohols in water and other ecofriendly solvents. A detailed discussion of catalytic cycles involving hypervalent iodine, hypoiodites, and. Oct 16, 2017 we anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis. The oxidation protocol using this chemoselective reagent is operationally simple, providing good to excellent yields of the carbonyl compounds. Hypervalent iodinehf reagents for the synthesis of 3. Hypervalent iodinev reagents, such as 2iodoxybenzoic acid ibx and dessmartin periodinane dmp, have found widespread synthetic application as stoichiometric oxidants for the facile and selective oxidation of alcohols to respective carbonyl compounds and also for some other important oxidative transformations. One such bond exists in iodineiii compounds and two such bonds reside in iodinev compounds. Oxidase catalysis via aerobically generated hypervalent. Tertiary amines atas are attractive structural motifs that are frequently found in biologically active molecules.
Oxidation of benzyl ethers to benzoate esters using a novel hypervalent iodine reagent arun p. When nucleoside chemistry met hypervalent iodine reagents. Recent advances in the development of environmentally friendly recyclable reagents and catalytic systems based on hypervalent iodine are discussed. Hypervalent iodineinduced oxidative couplings new metalfree coupling advances and their applications in natural product syntheses toshifumi dohi and. They can be used for various reactions with superior or similar reactivity as conventional hypervalent iodine iii reagents. Zhdankin department of chemistry and biochemistry, university of minnesota duluth, duluth, minnesota 55812, usa email.
The nature of iodine oxygen bonds in hypervalent 10i3 iodine compounds paul kiprof department of chemistry, university of minnesota duluth, duluth, mn 55812, usa. Transition metalfree coupling of terminal alkynes and. In addition, these reagents have found application in pdcatalyzed oxidation. Hypervalent iodine chemistry thomas wirth springer. Hypervalent iodineiii reagents in organic synthesis. Theoretical work is underpinning the development of novel compounds and catalysts, which have now already been established as powerful metalfree reagents. Oxidation of benzyl ethers to benzoate esters using a. This thematic series on hypervalent iodine chemistry covers all aspects and highlights current developments of this area.
Hypervalent iodineiii reagents in organic synthesis viktor v. Weaker and longer than covalent linkages, hypervalent bonds are the result of a linear threecenter, fourelectron 3c4e electronic distribution hypervalent model. This electrophilic intermediate may be attacked by a variety of nucleophiles or. Oct 03, 20 chapter 6 covers the green reactions of hypervalent iodine reagents under solventfree conditions or in aqueous solutions. Apr 14, 2018 the anodic oxidation of aryl iodides is a powerful method for the synthesis of hypervalent iodine reagents, which eliminates the necessity to use expensive or hazardous chemical oxidizing reagents. Use features like bookmarks, note taking and highlighting while reading hypervalent iodine chemistry. Preparation, structure, and synthetic applications of polyvalent. Hypervalent iodine reagents are useful synthetic tools due to their low toxicity, ready availability, and ease of handling. Veselya a department oforganic chemistry, faculty science, charles university in prague, hlavova 2030, 128 43 praha 2, czech. Hypervalent iodine iii compound synthesis by oxidation. They can be used for various reactions with superior or similar reactivity as conventional hypervalent iodineiii reagents. Therefore, the development of an efficient method for the synthesis of atas represents an important research topic in the field of medicinal chemistry as well as organic chemistry. The role of iodanyl radicals as critical chain carriers in. Hypervalent iodine reagents are useful synthetic tools due to.
We show that in contrast to the canonical twoelectron 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. Hypervalent iodinev reagents in organic synthesis uladzimir ladziata and viktor v. Recyclable reagents and catalytic systems based on. An excellent dual recycling strategy for the hypervalent iodine. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The intramolecular aminofluorination of homoallylamine derivatives using a reagent system of phioac2 and pyhf in ch2cl2 at room temperature for 5 h gave ntosyl3fluoropyrrolidines in good to high yields. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.
Recent advances in the development of environmentally friendly recyclable reagents and catalytic systems based on. Pdf hypervalent iodine reagents and green chemistry. The favorable reduction of the hypervalent iodide to. Hypervalent iodine iii reagents have been vastly used in many useful organic transformations. Hypervalent iodine reagents and green chemistry article pdf available in current organic synthesis 92. This book is aimed at all chemists interested in iodine compounds, including academic. The ringstrain energy of donor acceptor cyclopropanes was then used in the first catalytic formal homonazarov cyclization. Hypervalent iodine reagents have now become one of the most.
To summarize, this account focuses on the design, development, mechanistic understanding, and synthetic application of hypervalent iodineiii reagents in radical chemistry. Trapping of either product is possible with a suitable reagent, and this method is often employed in tandem with a second process. A great plethora of methods already exist to fulfill this task, and hypervalent iodine reagents belong to the most applied oxidation agents. There has been great interest in hypervalent iodine chemistry because of the use of hypervalent. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various. Hypervalent iodine induced oxidative couplings new metalfree coupling advances and their applications in natural product syntheses toshifumi dohi and yasuyuki kita phenol dearomatization with hy.
Hypervalent iodine reagents and green chemistry bentham science. Hypervalent iodine reagents and green chemistry buy article. In contrast to classical halogen bond donors based on iodine i compounds, iodine iii salts feature two electrophilic axes. Hypervalent iodine reagents for heterocycle synthesis and functionalization jiyun sun,1 daisy zhangnegrerie,2 yunfei du,1 kang zhao,1 1tianjin key laboratory for modern drug delivery and highefficiency, school of pharmaceutical science and technology, tianjin university, tianjin, 2concordia international school shanghai, shanghai, peoples republic of china abstract. Pdf 9 mb acs publications american chemical society. Zhdankin department of chemistry and biochemistry, university of minnesota duluth, duluth, minnesota 55812 email. Iodineiii reagents in radical chemistry accounts of. Chapter 6 covers the green reactions of hypervalent iodine reagents under solventfree conditions or in aqueous solutions. Julian lo hypervalent iodine baran group meeting 615 lil bond consists of an unhybridized p orbital 2 e come from iodine and 1 ecomes from each l, creating a 4 e, 3 center bond negative charge accumulates on each l. A green alternative to transition metals in organic chemistry and technology. Hypervalent iodine chemistry is the first comprehensive text covering all of the main aspects of the chemistry of organic and inorganic polyvalent iodine compounds, including applications in chemical research, medicine, and industry providing a comprehensive overview of the preparation, properties, and synthetic applications of this important class of reagents, the text is presented in the. Oxidase catalysis via aerobically generated hypervalent iodine.
This electrophilic intermediate may be attacked by a variety of nucleophiles or undergo rearrangement or elimination. Chapter 4 describes the most recent achievements in hypervalent iodine catalysis. The preparation, structure, and chemistry of hypervalent iodine compounds are. Hypervalent iodine compounds organic chemistry portal. A survey of chiral hypervalent iodine reagents in asymmetric. The applications of hypervalent iodine iii reagents in. Carbonyl oxidation with hypervalent iodine reagents wikipedia. When nucleoside chemistry met hypervalent iodine reagents mahesh k.
Iodine iii iodine v iodine vii the most electronegative ligands reside in the apical axial positions 1. Synthetic uses of hypervalent iodine reagents in halogenation. Pioneering metalfree oxidative coupling strategy of aromatic compounds using hypervalent iodine reagents. In order to accommodate the excess of electrons in hypervalent compounds the 3center4electron bond was introduced in analogy with the 3center2electron bond observed in electron deficient compounds. Pdf hypervalent iodineiii reagents in organic synthesis. A green alternative to transition metals in organic. In this study, the potential application of hypervalent iodine iii reagent was successfully extended to the dialkylation and cyclopropa enation of unsaturated alkenes and alkynes. Despite the environmentally benign characteristics of the hypervalent iodine reagent as a green oxidant, a general problem in its use in chemical reactions.
Phenol oxidation with hypervalent iodine reagents leads to the formation of quinonetype products or iodonium ylides, depending on the structure of the phenol. Carbonyl oxidation with hypervalent iodine reagents. Abstract development of sustainable oxidation chemistry demands strategies to. Hypervalent iodineiii compounds as biaxial halogen bond. Providing a comprehensive overview of the preparation, properties, and synthetic applications of this important class of reagents, the text is presented in the. Chapter 5 deals with recyclable polymersupported and nonpolymeric hypervalent iodine reagents. Synthesis and oxidation reactions of a user and ecofriendly. Aerobic hypervalent iodine chemistry provides a strategy for coupling the oneelectron chemistry of o2 with twoelectron processes typical of organic synthesis. The fast access to simple z3iodo acrylic acid derivatives which can be easily oxidized to the corresponding hypervalent iodineiii reagents is described. In combination with recyclable and reusable hypervalent iodine reactions, ruthenium catalysts could be used as a green and efficient catalytic oxidative system. It was shown that the main factor determining the p.
A variety of unsymmetrical 1,3diynes can easily be accessed in good yields under catalyst and transition metalfree conditions by reacting terminal alkynes with hypervalent iodine based electrophilic alkynetransfer reagents. Bjoc hypervalent iodine chemistry in organic synthesis. Hypervalent iodine chemistry in organic synthesis bjoc. Advances in synthetic applications of hypervalent iodine compounds. Similar reactivity was found for the zhdankin reagent that has been successfully applied to azidation of cradicals, and also cyanation is possible with a cyano iiii reagent. Oxidation of secondary alcohols using solidsupported. Furthermore, the catalytic aminofluorination was furnished by the reaction using piodotoluene as a catalyst in the presence of pyhf as a fluorine source and mcpba as a terminal oxidant. Hypervalent iodine chemistry by zhdankin, viktor v. Hypervalent iodine chemistry is the first comprehensive text covering all of the main aspects of the chemistry of organic and inorganic polyvalent iodine compounds, including applications in chemical research, medicine, and industry. General reactivity of hypervalent iodine n hypervalent iodine chemistry is based on the strongly electrophilic nature of the iodine making it suseptible to nucleophilic attack, in combination with the leaving group ability of phenyliodonio group iphx 106 times greater than triflate.
Hofmann rearrangement of carboxamides to carbamates using oxone as an oxidant can be efficiently catalyzed by iodobenzene. Hypervalent iodine, green chemistry, polymersupported reagents, catalysis, oxidation. Thottumkara, 1178 stacy lane, macomb, il 61455 macomb high school, macomb, il teacher andor mentor. Hypervalent iodine mediated paraselective fluorination of anilines cheminform 20, 44. Usa home product directory chemical synthesis synthetic reagents oxidizing agents hypervalent iodine chemistry products. Vinod hypervalent iodine reagents have found extensive use in synthetic organic chemistry as. Oxidation of benzyl ethers to benzoate esters using a novel. Introduction can theoretically proceed through either an associative or dissociative mechanism tetracoordinated species have been isolated, suggesting an associative mechanism i ar ll ll aryl.
Hypervalent iodine iiimediated decarboxylative ritter. For example, hypervalent iodine reagents are a broadly useful. The nature of iodine oxygen bonds in hypervalent 10i3. Organic chemistry arkivoc 2018, part ii, 252279 when nucleoside chemistry met hypervalent iodine reagents mahesh k. The hypervalent iodine reagents generated at the anode are successfully used as either in. This reaction involves hypervalent iodine species generated in situ from catalytic amounts of phi and oxone in the presence of 1,1,1,3,3,3hexafluoroisopropanol hfip in aqueous methanol solutions. Phenol oxidation with hypervalent iodine reagents organic.
Hypervalent iodine reagents and green chemistry bentham. Carbonyl oxidation with hypervalent iodine reagents involves the functionalization of the. The concept of hypervalent iodine was developed by j. Reactions of hypervalent iodine reagents with palladium.
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