A great plethora of methods already exist to fulfill this task, and hypervalent iodine reagents belong to the most applied oxidation agents. The role of iodanyl radicals as critical chain carriers in. 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. Oct 16, 2017 we anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis. In contrast to classical halogen bond donors based on iodine i compounds, iodine iii salts feature two electrophilic axes.
A detailed discussion of catalytic cycles involving hypervalent iodine, hypoiodites, and. This thematic series on hypervalent iodine chemistry covers all aspects and highlights current developments of this area. Synthesis and oxidation reactions of a user and eco. Hypervalent iodineiii reagents in organic synthesis. Use features like bookmarks, note taking and highlighting while reading hypervalent iodine chemistry. Hypervalent iodinev reagents in organic synthesis uladzimir ladziata and viktor v. Hypervalent iodine chemistry in organic synthesis bjoc. Thottumkara, 1178 stacy lane, macomb, il 61455 macomb high school, macomb, il teacher and or mentor.
Program in chemistry, the graduate center of the city university of new york. Hypervalent iodine reagents are useful synthetic tools due to their low toxicity, ready availability, and ease of handling. The preparation, structure, and chemistry of hypervalent iodine compounds are. 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. They can be used for various reactions with superior or similar reactivity as conventional hypervalent iodineiii reagents. Pdf hypervalent iodine reagents and green chemistry. 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. Preparation, structure, and synthetic applications of polyvalent.
Recyclable reagents and catalytic systems based on. Carbonyl oxidation with hypervalent iodine reagents. For example, iiii reagents have been used in place of aryl halides for diverse pdcatalyzed c. 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. This book is aimed at all chemists interested in iodine compounds, including academic. A green alternative to transition metals in organic. Hypervalent iodineiii compounds as biaxial halogen bond.
Zhdankin department of chemistry and biochemistry, university of minnesota duluth, duluth, minnesota 55812, usa email. Usa home product directory chemical synthesis synthetic reagents oxidizing agents hypervalent iodine chemistry products. 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. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. 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. Trapping of either product is possible with a suitable reagent, and this method is often employed in tandem with a second process.
The fast access to simple z3iodo acrylic acid derivatives which can be easily oxidized to the corresponding hypervalent iodine iii reagents is described. When nucleoside chemistry met hypervalent iodine reagents mahesh k. When nucleoside chemistry met hypervalent iodine reagents. Oxidation of benzyl ethers to benzoate esters using a novel hypervalent iodine reagent arun p.
The favorable reduction of the hypervalent iodide to. 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. Transition metalfree coupling of terminal alkynes and. The nature of iodine oxygen bonds in hypervalent 10i3 iodine compounds paul kiprof department of chemistry, university of minnesota duluth, duluth, mn 55812, usa. Zhdankin department of chemistry and biochemistry, university of minnesota duluth, duluth, minnesota 55812 email. The hypervalent iodine reagents generated at the anode are successfully used as either in. Hypervalent iodine iii compound synthesis by oxidation. Hypervalent iodineinduced oxidative couplings new metalfree coupling advances and their applications in natural product syntheses toshifumi dohi and. One such bond exists in iodineiii compounds and two such bonds reside in iodinev compounds.
Iodoxolonebased hypervalent iodine reagents organic letters. Aerobic hypervalent iodine chemistry provides a strategy for coupling the oneelectron chemistry of o2 with twoelectron processes typical of organic synthesis. Weaker and longer than covalent linkages, hypervalent bonds are the result of a linear threecenter, fourelectron 3c4e electronic distribution hypervalent model. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various. 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. Synthetic uses of hypervalent iodine reagents in halogenation. For example, hypervalent iodine reagents are a broadly useful. Hypervalent iodine chemistry thomas wirth springer. Theoretical work is underpinning the development of novel compounds and catalysts, which have now already been established as powerful metalfree reagents. Hypervalent iodine reagents are useful synthetic tools due to. Oxidation of benzyl ethers to benzoate esters using a. Thottumkara, 1178 stacy lane, macomb, il 61455 macomb high school, macomb, il teacher andor mentor. The nature of iodine oxygen bonds in hypervalent 10i3. Phenol oxidation with hypervalent iodine reagents organic.
In addition, these reagents have found application in pdcatalyzed oxidation. The unique reactivity of hypervalent iodine reagents with pd0 and pdii complexes has been exploited for a variety of synthetically useful organic transformations. The applications of hypervalent iodine iii reagents in. Pdf 9 mb acs publications american chemical society. 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. Vinod hypervalent iodine reagents have found extensive use in synthetic organic chemistry as. A green alternative to transition metals in organic chemistry and technology. Oct 03, 20 chapter 6 covers the green reactions of hypervalent iodine reagents under solventfree conditions or in aqueous solutions. Recent advances in the development of environmentally friendly recyclable reagents and catalytic systems based on hypervalent iodine are discussed.
This electrophilic intermediate may be attacked by a variety of nucleophiles or. Hypervalent iodine iiimediated decarboxylative ritter. Chapter 5 deals with recyclable polymersupported and nonpolymeric hypervalent iodine reagents. Iodineiii reagents in radical chemistry accounts of. 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. Chapter 6 covers the green reactions of hypervalent iodine reagents under solventfree conditions or in aqueous solutions. Organic chemistry arkivoc 2018, part ii, 252279 when nucleoside chemistry met hypervalent iodine reagents mahesh k. An excellent dual recycling strategy for the hypervalent iodine.
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. The obtained acetylenes are important building blocks for organic chemistry, material sciences and chemical biology. Hypervalent iodine reagents and green chemistry buy article. A survey of chiral hypervalent iodine reagents in asymmetric.
Pioneering metalfree oxidative coupling strategy of aromatic compounds using hypervalent iodine reagents. 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. It was shown that the main factor determining the p. Hypervalent iodine iii reagents have been vastly used in many useful organic transformations. The oxidation protocol using this chemoselective reagent is operationally simple, providing good to excellent yields of the carbonyl compounds. Oxidation of benzyl ethers to benzoate esters using a novel. 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.
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. They can be used for various reactions with superior or similar reactivity as conventional hypervalent iodine iii reagents. Hypervalent iodine reagents have now become one of the most. Hypervalent iodine reagents and green chemistry bentham science. Chapter 4 describes the most recent achievements in hypervalent iodine catalysis. Hofmann rearrangement of carboxamides to carbamates using oxone as an oxidant can be efficiently catalyzed by iodobenzene. Hypervalent iodine chemistry by zhdankin, viktor v. There has been great interest in hypervalent iodine chemistry because of the use of hypervalent.
Hypervalent iodine mediated paraselective fluorination of. 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. Oxidation of secondary alcohols using solidsupported. 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. 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. The fast access to simple z 3iodo acrylic acid derivatives which can be easily oxidized to the corresponding hypervalent iodine iii reagents is described. Hypervalent iodine mediated paraselective fluorination of anilines cheminform 20, 44. This electrophilic intermediate may be attacked by a variety of nucleophiles or undergo rearrangement or elimination. Abstract development of sustainable oxidation chemistry demands strategies to. 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. Carbonyl oxidation with hypervalent iodine reagents wikipedia.
Tertiary amines atas are attractive structural motifs that are frequently found in biologically active molecules. 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. 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. Hypervalent iodine compounds organic chemistry portal. Despite the environmentally benign characteristics of the hypervalent iodine reagent as a green oxidant, a general problem in its use in chemical reactions. A modified procedure for the direct synthesis of hypervalent bistrifluoroacetoxyiodoarenes avoids the use of hazardous reagents with the workup being only an aqueous extraction. Hypervalent iodine reagents for heterocycle synthesis and. Iodine iii iodine v iodine vii the most electronegative ligands reside in the apical axial positions 1. Oxidase catalysis via aerobically generated hypervalent iodine.
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. 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. The final chapter provides an overview of the important practical applications of polyvalent iodine compounds in medicine and industry. Phenol oxidation with hypervalent iodine reagents leads to the formation of quinonetype products or iodonium ylides, depending on the structure of the phenol. Hypervalent iodine reagents and green chemistry article pdf available in current organic synthesis 92. The ringstrain energy of donor acceptor cyclopropanes was then used in the first catalytic formal homonazarov cyclization. Veselya a department oforganic chemistry, faculty science, charles university in prague, hlavova 2030, 128 43 praha 2, czech. 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. Oxidase catalysis via aerobically generated hypervalent. Carbonyl oxidation with hypervalent iodine reagents involves the functionalization of the. Providing a comprehensive overview of the preparation, properties, and synthetic applications of this important class of reagents, the text is presented in the. Hypervalent iodinehf reagents for the synthesis of 3. In combination with recyclable and reusable hypervalent iodine reactions, ruthenium catalysts could be used as a green and efficient catalytic oxidative system. Recent advances in the development of environmentally friendly recyclable reagents and catalytic systems based on.
Reactions of hypervalent iodine reagents in green solvents and under. To summarize, this account focuses on the design, development, mechanistic understanding, and synthetic application of hypervalent iodineiii reagents in radical chemistry. Although the ritter reaction is a reliable approach for preparing. Hypervalent iodine, green chemistry, polymersupported reagents, catalysis, oxidation. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis. Pdf hypervalent iodineiii reagents in organic synthesis. 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. Hypervalent iodine reagents and green chemistry bentham. 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. 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. Bjoc hypervalent iodine chemistry in organic synthesis. The fast access to simple z3iodo acrylic acid derivatives which can be easily oxidized to the corresponding hypervalent iodineiii reagents is described. The concept of hypervalent iodine was developed by j. Hypervalent iodineiii reagents in organic synthesis viktor v.
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