Thioamination of alkenes with hypervalent iodine reagents. Chemistry a european journal 2016, 22 22, 75457553. Hypervalent refers to a main group element that breaks the octet rule and. The chemistry of hypervalent halogen compounds wiley. Hypervalent iodine chemistry is the first comprehensive text covering all of the main aspects of the chemistry of organic and inorganic. His current research interests focus on the chemistry of reactive intermediates and. Thomas wirth in the open access beilstein journal of organic chemistry. Here we demonstrate that anodically generated hypervalent iodine intermediates effectively couple interfacial electron transfer with oxidative chnh coupling chemistry. Zhdankin department of chemistry and biochemistry, university of minnesota duluth, duluth, minnesota 55812 email. Powers1,3, summary selective o 2 utilization remains a substantialchallenge in synthetic chemistry. Hypervalent iodine compounds tokyo chemical industry co.
Electrocatalytic cn coupling via anodically generated. Iodine is a largesized halogen element, easily polarizable, and low in electronegativity. Recyclable reagents and catalytic systems based on. Dubois nitrene chemistry proceeds through an iminoiodinane. Iodine can exist in high valence states because of its higher polarizability and smaller electronegativity compared with other halogen elements. Expanding the scope of hypervalent iodine reagents for perfluoroalkylation. 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. If you dont want to wait have a look at our ebook offers and start reading immediately.
Hypervalent iodine reagents are of considerable relevance in organic chemistry as they can provide a complementary reaction strategy to the use of traditional transition metal chemistry. Hypervalent iodine reagents are effective nonmetallic reagents 1, 2 that have found many applications as highly selective oxidants 3 and as electrophilic reagents 4 for various reactions, including rearrangements 5 and. Hypervalent iodine compounds are readily reduced to stable monovalent state with the dissociation. For example, iiii reagents have been used in place of aryl halides for diverse pdcatalyzed c. Hypervalent iodine chemistry modern developments in. The unique reactivity of hypervalent iodine reagents with pd0 and pdii complexes has been exploited for a variety of synthetically useful organic transformations. Mar 04, 2020 development of new electrosynthetic chemistry promises to impact the efficiency and sustainability of organic synthesis. Metalfree enantioselective oxidative arylation of alkenes. Hypervalent iodine reagents are useful synthetic tools due to. Hypervalent iodine chemistry thomas wirth springer. The hypervalent iodine reagents generated at the anode are successfully used as either in. Zhdankin department of chemistry and biochemistry, university of minnesota duluth, duluth, minnesota 55812, usa email.
Synthesis of 4selenoribonucleosides, the building blocks. Expanding the scope of hypervalent iodine reagents for. Nov 22, 20 chiral hypervalent iodine chemistry has been steadily increasing in importance in recent years. Apr 14, 2018 the hypervalent iodine reagents generated at the anode are successfully used as either in. Hypervalent iodine reagents are useful synthetic tools due to their low toxicity, ready availability, and ease of handling.
Phenol oxidation with hypervalent iodine reagents wikipedia. 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. Advances in synthetic applications of hypervalent iodine. Access to hypervalent iodine compounds a class of broadly useful chemical oxidants from o2 increases the scope of aerobic oxidation chemistry that can be achieved. The understanding of functional groups is the key to understanding organic chemistry. Structural chemistry of hypervalent iodine compounds. Advances in hypervalent iodine chemistry have put the field on the precipice of a second golden age. Structure and reactivity of hypervalent iodine compounds are generally similar to that of the transition metal. Hypervalent iodine reactions utilized in carboncarbon bond. Organic chemistry arkivoc 2018, part ii, 252279 when nucleoside chemistry met hypervalent iodine reagents mahesh k. Phenol oxidation with hypervalent iodine reagents leads to the formation of quinonetype products or iodonium ylides, depending on the structure of the phenol.
It forms hypervalent iodine compound beyond the octet rule by. We report a unified photoredoxcatalysis strategy for both hydroxylation and amidation of tertiary and benzylic ch bonds. Hypervalent iodine compounds organic chemistry portal. The role of iodanyl radicals as critical chain carriers in. 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.
Yet the benchstable hypervalent iodine form of togni reagent i was much higher in energy than the ether. A mechanistic hypothesis is presented that rationalizes the reaction pathways and. Compounds of iodine possess reactivity similar to that of transition metals, but have the advantage of environmental sustainability and efficient utilization of natural resources. Article the role of iodanyl radicals as critical chain carriers in aerobic hypervalent iodine chemistry sungmin hyun,1 mingbin yuan,2 asim maity,1 osvaldo gutierrez,2, and david c. Use features like bookmarks, note taking and highlighting while reading hypervalent iodine chemistry. In particular, the ability to use these species in place of expensive or toxic metal salts is appealing. Oxidase catalysis via aerobically generated hypervalent. In 2006, he was promoted to associate professor at the university of hyogo. 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.
Merging hypervalent iodine and sulfoximine chemistry. Weaker and longer than covalent linkages, hypervalent bonds are the result of a linear threecenter, fourelectron 3c4e electronic distribution hypervalent model. The reaction pathway for each transformation was shown to be a function of reagent stoichiometry. Chiral hypervalent iodinecatalyzed enantioselective oxidative kita spirolactonization of 1naphthol derivatives and onepot diastereoselective oxidation to epoxyspirolactones muhammet uyanik, takeshi yasui, kazuaki ishihara. Electrophilic trifluoromethylation is at the forefront of methodologies available for the installation of the cf3 moiety to organic molecules.
Hypervalent iodine chemistry by zhdankin, viktor v. School of chemistry, cardiff university, park place, main building, cardiff, cf10 3at uk. Hypervalent iodine reagents aversion to conversion. Fujita and coworkers described a stereoselective oxylactonization reaction in the presence of a chiral hypervalent iodine catalyst 47,48. 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 developed hypervalent iodine electrocatalysis is applicable in both intra and intermolecular c. In the past two decades, a number of organic chemists used these reagents. When nucleoside chemistry met hypervalent iodine reagents mahesh k. Providing a comprehensive overview of the preparation, properties, and synthetic applications of this important class of reagents, the text is presented in the. Hypervalent iodine chemistry in organic synthesis is a thematic issue edited by prof. In the tradition of patais chemistry of functional groups each volume treats all aspects of functional groups, touching on theoretical, analytical, synthetic, biological, and industrial aspects. Hypervalent iodine chemistry, recent advances and applications. Special issue advances in the chemistry of hypervalent.
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. Hypervalent iodine compounds are useful reagents in organic chemistry e. Hypervalent halogen compounds, in particular iodine compounds, are very efficient and selective oxidants which. More recently, recyclable mediators and catalytic protocols have been developed. Pdf 9 mb acs publications american chemical society. Chiral hypervalent iodine chemistry has been steadily increasing in importance in recent years. Hypervalent iodinev reagents in organic synthesis uladzimir ladziata and viktor v. Synthetic uses of hypervalent iodine reagents in halogenation reactions, various oxidations, rearrangements, aminations, cc bond forming reactions, and transition metal.
Providing a comprehensive overview of the preparation, properties, and synthetic applications of this important. Preparation, structure and synthetic applications of polyvalent iodine compounds. Hypervalent iodine chemistry in organic synthesis bjoc. Pdf on dec 5, 20, viktor zhdankin and others published hypervalent iodine chemistry. 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 carboncarbon bondforming reactions. Aerobic hypervalent iodine chemistry provides a strategy for coupling the oneelectron chemistry of o2 with twoelectron processes typical of organic synthesis. Hypervalent iodineiii reagents in organic synthesis. Bjoc hypervalent iodine chemistry in organic synthesis. Dessmartin periodinane tetra, penta and hexavalent phosphorus, silicon, and sulfur compounds ex. Preparation, structure, and synthetic applications of polyvalent.
These compounds are widely used in organic synthesis as selective oxidants and. The concept of hypervalent iodine was developed by j. From trifluoromethyl to functionalized perfluoroethyl dr. Phosphorus pentachloride pcl 5, sulfur hexafluoride sf 6, chlorine trifluoride clf 3, the chlorite clo 2. Synthesis of spirocyclic scaffolds using hypervalent. Several specific classes of hypervalent molecules exist.
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. When nucleoside chemistry met hypervalent iodine reagents. This thematic series on hypervalent iodine chemistry covers all aspects and highlights current developments of this area. Hypervalent iodinemediated fluorination of styrene derivatives. Hypervalent iodine chemistry modern developments in organic synthesis.
Most notable are the monograph by varvoglis6 on the application of hypervalent iodine compounds in organic synthesis and the volume of topics in current chemistry34 on hypervalent iodine chemistry. Over the past two decades, there have been an increasing number of applications including stoichiometric oxidation and catalytic asymmetric variations. 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. Pcl 5, pf 5, sf 6, sulfuranes and persulfuranes noble gas compounds ex. Hypervalent iodine in organic synthesis 1st edition. Your print orders will be fulfilled, even in these challenging times. Tetrahedron hypervalent iodine chemistry, recent advances. Reactions of hypervalent iodine reagents with palladium. Total synthesis of natural products using hypervalent. Additionally, mcpba and trifluoroacetic acid were utilized as terminal oxidants and activators, respectively. Here we demonstrate that anodically generated hypervalent iodine intermediates effectively couple interfacial electron transfer with oxidative c hnh coupling chemistry. It forms hypervalent organoiodanes beyond the octet theory by readily extending its valence. Hypervalent iodine compounds synthetic reagents tokyo.
One such bond exists in iodineiii compounds and two such bonds reside in iodinev compounds. Trapping of either product is possible with a suitable reagent, and this method is often employed in tandem with a second process. Total synthesis of natural products using hypervalent iodine. A hypervalent molecule the phenomenon is sometimes colloquially known as expanded octet is a molecule that contains one or more main group elements apparently bearing more than eight electrons in their valence shells. Here, we report that oneelectron oxidation reactions pathways via iodanyl radical intermediates are critical in aerobic hypervalent iodine chemistry. The fivemembered ring ought to fall apart with the energy it has, yet somehow it doesnt, schaefer tells chemistry world. 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 new appreciation for the critical role that iodanyl radicals can play in the synthesis of hypervalent. 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 iii reagents in organic synthesis viktor v. Hypervalent iodine compounds bearing a sulfoximine group have previously been reported by bolm and coworkers, however the reported compounds were designed for the transfer of the sulfoximine moiety, and hence not a part of the 5membered heterocycle. Hypervalent iodineiii reagents in organic synthesis viktor v. Hypervalent iodine chemistry modern developments in organic.
The reaction with silylated uracil affords the desired 4selenouridine derivatives with excellent selectivity and in good yield. Hypervalent iodine reagents for heterocycle synthesis and. Use of hydroxyl perfluorobenziodoxole pfbloh oxidant is critical for efficient tertiary ch functionalization, likely due to the enhanced electrophilicity of the benziodoxole radical. Program in chemistry, the graduate center of the city university of new york. The chemistry of hypervalent iodineiii compounds in organic synthesis was thought to be broadened by employing products from the developed protocols in. So how can such a highlystrung compound be available to buy in a bottle. Oct 16, 2017 access to hypervalent iodine compounds a class of broadly useful chemical oxidants from o2 increases the scope of aerobic oxidation chemistry that can be achieved. 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. Iodine is atomic number 53, in the 5th period, group 17, halogens of the periodic table. Hypervalent iodine chemistry has matured over several decades, with many transformations mediated by hypervalent iodine compounds now being commonplace in synthesis. The developed hypervalent iodine electrocatalysis is applicable in both intra and intermolecular cn bondforming reactions. Chapter 3, the central chapter of the book, deals with applications of hypervalent iodine reagents in organic synthesis. Development and applications of hypervalent iodine compounds.
Hypervalent iodine chemistry is in constant growth, and these strategies are only examples of the expanding literature on the applications of hypervalent iodine reagents in the synthesis of natural products. The favorable reduction of the hypervalent iodide to. This book describes the fascinating chemistry of the many kinds of organic compounds of hypervalent iodine. 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. Stoichiometric and catalytic transformation to 2,2difluoroethylarenes. Biological smallmolecule oxidation reactions often utilize aerobically gener. Hypervalent iodinemediated fluorination of styrene. Treatment of 1,4dimethoxynaphthalenes with iodosobenzene diacetate and trimethylsilyl chloride or bromide furnished the haloacetoxylated, acetoxylated, and halogenated 1,4dimethoxynaphthalenes in excellent yield. Hypervalent iodine iii fluorinations of alkenes and diazo compounds. Oct 03, 20 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. Abstract the anodic oxidation of aryl iodides is a powerful method for the synthesis of hypervalent iodine reagents.
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