This thematic series on hypervalent iodine chemistry covers all aspects and highlights current developments of this area. Each chapter deals with a particular iodine compound or families of compounds which have been used as reagents in a plethora of useful transformations. Hypervalent iodine in organic synthesis best synthetic. Among them, hypervalent iodine reagents have found major use and applications.
In the past decade, the organic chemistry of iodine has experienced a rapid development. Their environmentfriendly nature and mild reaction conditions makes them more attractive candidates for the replacements of various toxic metals in organic synthesis 1831. Department of chemistry,university of minnesota duluth, duluth, minnesota 55812, usa. Hypervalent iodineiii reagents in organic synthesis. For some years our group has been interested in studying the io bond and the dynamical behavior of some important i iii and i v organic derivatives. Benziodoxolebased hypervalent iodine reagents in organic. Pdf download hypervalent iodine in organic synthesis free. 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. Nucleophilic substitution of psubstituted phenol ethers yasuydu kita, takeshi takada, and hirofumi tohma faculty of pharmaceutical sciences, osaka university, 16 yamadaoka, suita, osaka 565, japan abstract. Applications of hypervalent iodine reagents and iodonium ylides in organic synthesis date. T1 hypervalent iodine iii reagents in organic synthesis.
Bjoc hypervalent iodine chemistry in organic synthesis. Hypervalent iodine chemistry modern developments in organic synthesis. Without modifier, iodane is the systematic name for the parent hydride of iodine, hi. Chapter 3, the central chapter of the book, deals with applications of hypervalent iodine reagents in organic synthesis. Basic oxidations of alcohols to the corresponding carbonyl compounds.
We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis. The hypervalent iodine reagents generated at the anode are successfully used as either in. 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. Can oxidize allylic alcohols to enals with ibx and do wittigs in one pot yadav, synth. Hypervalent iodine chemistry is a field of great interest as shown by the large body of literature dealing with its various aspects1 2 3456. Hypervalent iodine reagents for tosyl transfer reactions.
Biochemie biochemistry inorganic chemistry organic chemistry organische chemie oxidation rearrangement natural. Hypervalent iodinehf reagents for the synthesis of 3. This book describes the fascinating chemistry of the many kinds of organic compounds of hypervalent iodine. Hypervalent iodine reagents are useful synthetic tools due to their low toxicity, ready availability, and ease of handling. Hypervalent iodine reagents in organic synthesis hypervalent. Hypervalent iodine reagents in organic synthesis 1 hypervalent iodine reagents in organic synthesis. Development and applications of hypervalent iodine. Hypervalent iodine chemistry organic chemistry portal. To access a cheminform abstract, please click on html or pdf.
Structure and reactivity of hypervalent iodine compounds are generally similar to that of the transition metal. Hypervalent iodine compounds organic chemistry portal. Hypervalent iodine chemistry thomas wirth springer. Applications of hypervalent iodine reagents in organic synthesis date. Thus, any organoiodine compound with general formula ri e. 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.
Each synthetic route features a phenol dearomatization promoted by an environmentally benign hypervalent iodine reagent. In early work on chiral hypervalent iodine reagents wirth devised an enantioselective dioxygenation reaction under stoichiometric conditions,16 which was later extended using the chiral bislactate derivative 1. The unique reactivity of hypervalent iodine reagents with pd0 and pdii complexes has been exploited for a variety of synthetically useful organic transformations. Iodane generally refers to any organic derivative of iodine. Advances in synthetic applications of hypervalent iodine compounds. Benziodoxolebased hypervalent iodine reagents in organic synthesis volume. Hypervalent iodine in organic synthesis sciencedirect. Hypervalent iodine in organic synthesis 1st edition. Purchase hypervalent iodine in organic synth esis 1st edition. The new mode of reactivity allows various diaryliodonium triflates to be accessed, simply by heating a mixture of electron deficient diaryliodonium triflate with a moderately electron. Synthesis of spirocyclic scaffolds using hypervalent.
Each chapter deals with a particular iodine compound or families of compounds which have. 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. Hypervalent iodine reagents for heterocycle synthesis and. Hypervalent iodine in organic synth esis best synthetic methods 1st edition. 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. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. In addition, these reagents have found application in pdcatalyzed oxidation. Hypervalent iodine reagents provide various functional group transformation opportunities in organic chemistry. Iodine iii at the hypervalent state is known to be a good leaving group and in the case of a, ci cleavage is favorable 3. Applications of hypervalent iodine reagents in organic.
Journal of the chinese chemical society 2009, 56 3, 632635. Hypervalent iodine chemistry by zhdankin, viktor v. His main research interests are in the fields of synthetic and mechanistic organic chemistry of hypervalent maingroup elements iodine, xenon, selenium, sulfur, and phosphorus, organofluorine chemistry, and chemistry of acetylenes. Hypervalent iodine iii sulfonate mediated synthesis of 2arylimidazo1,2 a pyrimidines in liquid peg400. Hypervalent iodine in organic synth esis issn and millions of other books are available for amazon kindle. However, as used in the context of organic synthesis, the term iodane more specifically refers to organoiodine compounds with nonstandard bond. Hypervalent iodine in organic synthesis book, 1997. This growing interest in iodine compounds is mainly due to the mild and.
Pdf hypervalent iodineiii reagents in organic synthesis. Fivemembered hypervalent iodine heterocycles derived from benziodoxole and. Providing a comprehensive overview of the preparation, properties, and synthetic applications of this important class of reagents, the text is. Within the broad field of hypervalent iodine chemistry, organoiodinev reagents occupy a special place. Purchase hypervalent iodine in organic synthesis 1st edition. Hypervalent iodine chemistry modern developments in. Hypervalent iodinev reagents in o rganic synthesis hypervalent iodinev reagents in o rganic synthesis ladziata, uladzimir. The present volume is the first in the series to survey the properties and chemical behaviour of hypervalent iodine and bromine, their use in organic synthesis, as well as their industrial application. Ppt hypervalent iodine reagents in organic synthesis.
It was first prepared by willgerodt by disproportionation of iodosylbenzene under steam distillation to iodylbenzene and iodobenzene. A varvoglis this book describes the fascinating chemistry of the many kinds of organic compounds of hypervalent iodine. Contemporary organic synthesis hypervalent iodine in organic synthesis. Hypervalent iodine in organic synthesis 1st edition elsevier. Weaker and longer than covalent linkages, hypervalent bonds are the result of a linear threecenter, fourelectron 3c4e electronic distribution hypervalent model. In the first part, a novel reactivity of diaryliodonium triflates towards aryl iodides will be discussed. Oxidase catalysis via aerobically generated hypervalent.
The novel hypervalent iodine induced nucleophilic substitution of p. Find all the books, read about the author, and more. The inter est in these compounds originated in 1983. Hypervalent iodine reagents in organic synthesis request pdf.
Organic iodine iii and iodine v derivatives are now routinely used in organic synthesis as reagents for various selective oxidative transformations of complex organic molecules. The electrophilic properties of these reagents can also be used to introduce other functionalizations. 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. Summary chapter 3, the central chapter of the book, deals with applications of hypervalent iodine reagents in organic synthesis.
Utilizing kosers framework new heterocyclic hypervalent iodine reagents have been synthesized using 2iodobenzoic acid as well as other similar substrates as a starting material along with htib. In contrast, understanding of the reactivity of halogeni species in the presence of lewis bases, and their reaction mechanisms, are very limited. 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. Many types of hypervalent iodine reagents have been used to organic synthesis.
These include assorted oxidation, such as with the precious dessmartin reagent. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, cc bond forming reactions, and transition metal. Hypervalent iodine in organic synthesis ebook, 1997. For example, iiii reagents have been used in place of aryl halides for diverse pdcatalyzed c. Hypervalent iodine iii reagents in organic synthesis. This thesis discloses two different applications of hypervalent iodine iii reagents in organic synthesis. Hypervalent iodine species that exceed eight electrons in the valence shell. The dearomatizations demonstrate the aromatic ring umpolung concept, and involve stereoselective remodeling of the inert unsaturations of a phenol into a highly.