It provides a thorough overview of the synthesis and characterization of different types of chiral ferrocene ligands. Wirth, in comprehensive organometallic chemistry iii, 2007. This book describes and illustrates different synthetic routes to organic structures using selenium reagents or intermediates. Seleniummediated synthesis of biaryls through rearrangement. Seleniumiv oxide and seleniciv acid as oxidizing agents and oxidation catalysts the first publication on the use of seleniumiv oxide in oxidation reactions appeared in 1932 27 and since. Boranes for organic reductionsa fortyyear odyssey purdue university. Oxidation reactions play an important role in modern organic chemistry and during the recent decades, several methods have been developed in response to an increasing demand for. Many of these methods are currrently been used as standard. Studies on bioactive seleniumcontaining organophosphorus. Hypervalent iodineiii reagents in organic synthesis. Selenium belongs with oxygen and sulfur to the group 16 elements or chalcogens, and similarities in chemistry are to be expected selenium can exist with oxidation state. Hypervalent iodineiii reagents in organic synthesis viktor v. Selenium compound an overview sciencedirect topics.
Selenium stabilized carbenium ions on organic synthesis. Electrophilic selenium catalysis with electrophilic nf. Seleniumcontaining reagents and organoselenium compounds play an important role in modern organic synthesis 714. The development has been catalyzed by technical and biological interest in sulfur and selenium compounds, and the study of their. Reaction intermediates in organic chemistry the big picture1 john andraos abstract. The purpose of this text is to provide a survey, and systematic introduction to, the modern techniques of organic synthesis for the advanced undergraduate student or the beginning graduate student. These mainly involve the invention of selenium and tellurium reagents, and the development of radical cyclization, which is an area that has become an extremely valuable part of synthetic organic chemistry. Benzeneselenenyl reagents in organic synthesis article pdf available in journal fur praktische chemie 3403. Developments in the chemistry of selenaheterocyclic compounds. The unique qualities of organoselenium reagents and compounds were poorly. Review of organoselenium chemistry between synthesis and. In the last years there has been a considerable development of selenium based methods for organic synthesis 1. Besides the use of electrophilic or nucleophilic selenium reagents in synthesis, selenium has another advantage.
An attempt has been made to acquaint the student with a. Modern radical methods and their strategic applications in synthesis burgenstock special section 2017 future stars in organic chemistry modern strategies for borylation in synthesis. It can stabilize adjacent carbanions or carbocations. For example it has been reported that the redness selenium nanoparticles has high biological activities and low toxicity 12 and nanowires of trigonal selenium have novel photoconductivity. The scope ranges from the preparation of both inorganic and organic selenium reagents, through descriptions of structure, toxicity, biological aspects and nuclear magnetic resonance, to applications. These mainly involve the invention of selenium and tellurium reagents, and the development of radical cyclization, which is an area that has become an extremely valuable. The approach emphasizes that such transformations are simple, efficient and often carried out at room temperature. Since then many applications of silicon, tin, phosphorus, sulfur, selenium, and other metalloids in. The book starts by presenting some of more efficient ways to. Once chemists began amassing a library of chemical reactions that made it possible for one chemical structure to be transformed into another, thereby ushering in the vast and unlimited field of organic synthesis, it soon became apparent that patterns of reactivity among common structures emerged as a consequence of. Since then many applications of silicon, tin, phosphorus, sulfur, selenium, and other metalloids in organic syn thesis have been proposed. Application of metalation reactions for synthesis of new.
Selenium iv oxide and seleniciv acid as oxidizing agents and oxidation catalysts the first publication on the use of selenium iv oxide in oxidation reactions appeared in 1932 27 and since then it has been applied as a versatile reagent for the synthesis of various types of organic compounds 12,2325,2830. From alkenes both tomoda15 and seebachlg have utilized selenium chemistry in the preparation of nitroalkenes. Selenium dioxide cas 7446084 845008 merck millipore. Selenium radical ions in organic synthesis springerlink. The most commonly used oxidant for selenium compounds is h 2 o 2. Zhdankin department of chemistry and biochemistry, university of. The rest of the storya daily occurrence throughout much of the nation is the broadcast of the news and commentary by paul harvey, a colorful, enthusiastic and extremely conservative journalist who includes in his reports a tersely worded news item recently featured by one of the major wire services and then proceeds. Synthetically useful organic reactions or reagents are often referred to by the name of the discoverers or developers. Selenaheterocyclic compounds of practical importance 3. Selenium radical anions are suggested to be the reactive intermediates in the reductive cleavage of aryl alkyl, vinyl alkyl or vinyl acyl selenides.
Organoselenium compounds are chemical compounds containing carbonto selenium chemical bonds. Reaction intermediates in organic chemistry the big. A simple wet chemical method has been developed to synthesize selenium nanoparticles size 40100 nm, by the reaction of sodium selenosulphate precursor with different organic acids in aqueous. Developments in synthetic application of seleniumiv. Save up to 80% by choosing the etextbook option for isbn. Developments in synthetic application of seleniumiv oxide.
An organic acidinduced synthesis and characterization of. Organoselenium chemistry has become an important tool in synthetic and medicinal chemistry. Buy selenium reagents and intermediates in organic synthesis organic chemistry on free shipping on qualified orders. Selenium compounds as ligands and catalysts springerlink. European journal of organic chemistry 2010, 2010 29, 56015606. Claude paulmier the explosive growth of organoselenium chemistry over the past 12 years can be attributed to the specific properties of organic selenium molecules, which fit the requirements of modern organic. Selenium belongs with oxygen and sulfur to the group 16 elements or chalcogens, and similarities in chemistry are to be expected. In selenium reagents and intermediates in organic synthesis vol. Recent developments in homobimetallic reagents and catalysts. Trivalent selenium compounds such as seleniranium derivatives of type 34 and 35 are intermediates which are frequently used in organic synthesis, although these intermediates are usually instable and. Various seleniumcontaining compounds are widely used as reagents and intermediates in organic synthesis. Selenium reagents for organic synthesis university of alberta 3 block, eric organic sulfur compounds in organic synthesis.
Molecules free fulltext electrophilic selenium catalysis. The total syntheses of neolemnane and 14deoxyisoamijiol. Selenium can be introduced as an electrophile, as a nucleophile, or as a radical. Selenium reagents and intermediates in org anic synthesis. Selenium mediated synthesis of biaryls through rearrangement. Recent developments in homobimetallic reagents and catalysts for organic synthesis.
Heterocycles with selenium atoms in the ring, such as selenirenes, selenophenes, benzselenophenes, selenadiazoles, selenatriazoles, benzisoselanazolones, and in combination with other heteroatoms such as n, o, and s in the ring, act as reagents and intermediates employed in the synthesis of alkenes and alkynes. Zhdankin department of chemistry and biochemistry, university of minnesota duluth, duluth, minnesota 55812, usa email. Organoselenium chemistry is the corresponding science exploring their properties and reactivity. Catalytic cycle is initiated via formation of an intermediate 4 by the reaction of alcohol 1. Older name reactions are described, isbn 9780080402802 buy the organic syntheses based on name reactions and unnamed reactions ebook. Functional group manipulation usin organoselenium reagents. This book meets the longfelt need for a reference on ferrocenes with the focus on catalysis. The scope ranges from the preparation of both inorganic and organic selenium reagents, through descriptions of structure, toxicity, biological aspects and nuclear magnetic resonance, to applications of specific selenium compounds in various syntheses including natural products and biologically active compounds. Selenium stabilized carbenium ions on organic synthesis scielo. The potential for introducing selenium into a range of electrophilic substrates and applications in organic synthesis are highlighted in section 9. Recent developments in homobimetallic reagents and. Organoselenium compounds are chemical compounds containing carbon to selenium chemical bonds. The purpose of this text is to provide a survey, and systematic introduction to, the modern techniques of organic synthesis. Organoselenium compounds are chemical compounds containing carbontoselenium chemical bonds.
Synthesis and reactivity of 3alkynyldihydroselenophene derivatives. The book starts by presenting some of more efficient ways to introduce an organoselenium group to an organic substrate, including electrophilic and nucleophilic selenium reagents. Reagents, catalysts and intermediates in synthesis of nonselenium compounds during last thirty years the longstanding but modest use of selenium reagents by organic synthetic chemists received a new. Solidphase synthesis of 3hydroxy2methylenealkanenitriles. Organoselenium chemistry has become widely used in organic synthesis, because of the availability of both electrophilic and nucleophilic selenium species. Reaction intermediates in organic chemistry the big picture. Developments in the chemistry of selenaheterocyclic. A suitable oxidative system is crucial to electrophilic selenium catalysis esc. More commonly, organic selenium reagents are used to catalyse organic reactions, but. In addition, polymersupported reagents offer further advantages that include reaction of active intermediates by catchandrelease, selectivity and immobilization of toxic intermediates. Claude paulmier the explosive growth of organoselenium chemistry over the past 12 years can be attributed to the specific. Older name reactions are described, isbn 9780080402802 buy the organic syntheses. Until recently, selenium derivatives at a higher oxidation state had found rather limited use in organic synthesis. Sakae uemura, in comprehensive organic synthesis, 1991.
Compounds containing a selenium atom at a higher oxidation state have, apart from selenium. Selenium reagents and intermediates in organic synthesis. The last ten years, however, have shown that these species are valuable reagents. It provides a thorough overview of the synthesis and characterization of different types of chiral ferrocene ligands, their application to various catalytic asymmetric reactions, and versatile chiral materials as well as drug intermediates synthesized from them. Seleniumiv oxide and seleniciv acid as oxidizing agents and oxidation catalysts the first publication on the use of seleniumiv oxide in oxidation reactions appeared in 1932 27 and since then it has been applied as a versatile reagent for the synthesis of various types of organic compounds 12,2325,2830. Reagents, catalysts and intermediates in synthesis of nonselenium compounds during last thirty years the longstanding but modest use of selenium reagents by organic synthetic chemists received a new impetus. Peculiarities in the reactivity of telluriumorganic compounds in comparison with their sulfur and selenium analogs. Page 26 general papers arkivoc 2006 ix 2658 hypervalent iodinev reagents in organic synthesis uladzimir ladziata and viktor v. Several highly selective transformations of alkenes such as allylic or vinylic imidation, pyridination, syndichlorination, oxidative cyclization and asymmetric cyclization have been described.
163 1171 519 134 167 1006 192 983 1271 1190 115 280 1237 148 1523 1435 691 86 129 110 294 1238 408 3 926 323 1322 1377 1128 928 341 581 583 1176 427 1438 1034 629 768 1450 530 735 787 744 1169 412