Crosscoupling reactions using samariumii iodide chemical. Synthesis of nitrogen heterocycles using samariumii iodide mdpi. Organic synthesis using samarium diiodide a practical guide. Search results for samarium iodide at sigmaaldrich. His research interests lie in the development of organic reactions and their. Smi2 is a versatile reagent now widely used in organic chemistry. Additional applications of smi 2 include pinalol coupling, alkylcarbonyl coupling, deoxygenation, the reformatsky reaction, and freeradical mediated cyclization. Applications of samarium iodide reagent to reduce alkyl halide to alkane,ketones and aldheydes to alcohols with complete explaination by various examples. Organic preparations and procedures international 2003, 35 3, 307360. Samariumii iodide is an inorganic compound with the formula smi2. When employed as a solution for organic synthesis, it. In the three decades since the first explorations of the synthetic utility of samarium diiodide smi 2, its importance in organic synthesis has grown significantly. Samariumii iodide mediated cyclizations in natural product synthesis the kagan reagent part ii an evans group afternoon seminar keith fandrick seminar outline. Samarium ii iodide solution is available in standard form as a 0.
Preparation and use of samarium diiodide smi2 in organic synthesis. Smi2 is a green solid and its solutions are green as well. Fabrice denes, mark pichowicz, guillaume povie, and philippe renaud. Spectrum chemical manufactures and distributes fine chemicals with quality you can count on including those with cas number 32248434, you can be assured that all samarium ii iodide products offered by spectrum, meet or exceed the grade requirements or specifications for each individual product. Full text of samarium diiodide reactions of alphaoxygenated carbonyls see other formats samarium diiodide reactions of alpha oxygenated carbonyls by jeffrey a. Despite the wealth of literature on the subject, the mechanisms of some smi2mediated reactions are still uncertain and the role of additives and cosolvents is poorly understood. Financial support of our program by rutgers university is gratefully acknowledged. Samarium oxide is used in optical glass to absorb infrared light. Samarium ii iodide solution smi 2 can be used as a reagent in the synthesis of. Since that time, samarium iodide has been employed in a variety of contexts in organic synthesis for both functional group manipulation and carboncarbon bond formation. Samarium compounds act as sensitizers for phosphors excited in the infrared.
However, it remains the responsibility of the readers to familiarize themselves with the product information contained on the us product label or package insert. Samariumii iodide smi 2 is a mild oneelectron reducing agentused for various reductive reactions of carbonyl compounds, organic halides, and electron deficient olefins. A novel and efficient samarium iodidemediated synthesis of. Recent studies on samarium diiodide mediated organic synthesis. Benzannulated pyrrolizidines and indolizidines by smi 2induced cyclizations of indole derivatives. The journal of organic chemistry 2014, 79 6, 25222537. Samariumii iodide mediated cyclizations in natural product. Preparation and use of samarium diiodide smi 2 in organic synthesis. Samarium ii iodide promoted synthesis of preferentially zolefins, including zhaloalkenes 3 in which the halogen can be cl, br, or i, through a. Psd were measured using sigma scan pro software jandel scientific. Samariumiimediated reactions in organic synthesis method. Synthesis of nitrogen heterocycles using samarium ii iodide. Smi 2 is a green solid and its solutions are green as well. It is noteworthy that three separate total syntheses of taxol 41, see schemes 10,25, 25, and and30 30 employed smi 2 for unrelated transformations.
Samarium ii iodide is used as a chemical reagent in organic synthesis, for example in the barbier reaction. It is a strong oneelectron reducing agent that is used in organic synthesis. But when combined with hmpa, samarium iodide is also capable of bringing about. Structure, properties, spectra, suppliers and links for. Samarium diiodidemediated reactions in total synthesis ncbi. Historically, the use of smi2 in organic synthesis has been focused on the. Molybdenumcatalysed ammonia production with samarium. Introduction and backgroundintramolecular barbier reactionintramolecular reformatsky reactionradical alkene and alkyne cyclizationscarbonylalkene reductive cyclizations. Application of aluminum triiodide in organic synthesis.
Enantioselective cyclizations and cyclization cascades of. Samariumii iodide smi 2 is a green solid composed of samarium and iodine, with a melting point of 520 c. The mechanistic role of hmpa and niii salts in the samarium barbier. Full text of samarium diiodide reactions of alphaoxygenated. In 1979, kagan observed the reduction of a variety of organic functional groups by samarium iodide under mild conditions. Samariumii iodide smi 2, also known as kagan reagent is a green solid composed ofsamarium and iodine, with a melting point of 520 c where the samarium atom has acoordination number of seven in a capped octahedral configuration. When employed as a solution for organic synthesis, it is.
Samariumii iodide mediated intramolecular aldoltype. Mild preparation of samarium iodide and ytterbium iodide and their use. Reactions of samariumii iodide with carbohydrate derivatives 470 iv. General characteristics samarium ii iodide smi2 is a mild oneelectron reducing agent used for various reductive reactions of carbonyl compounds, organic halides, and electron deficient olefins. In addition, samarium diiodide can mediate such a wide variety of organic chemistry that potential new users are often overawed by the extensive primary literature on the reagent. Samariumii iodide solution smi 2 can be used as a reagent in the synthesis of.
Protonation accepting a proton from a suitable donor is a characteristic reaction of an organosamarium compound. Every effort has been made to ensure the accuracy of the organic iodide powder information published above. Samariumii iodide is an inorganic compound with the formula smi 2. Preparation and use of samarium diiodide smi2 in organic. The paterson synthesis does not have such a nonselective step but still requires 6 equivalents of samarium iodide, why are 6 equivalents necessary. He is the principal author of more than 40 publications on the use of samarium diiodide and other transition metal based single electron reagents in organic synthesis since 1994. Feb 04, 20 divalent lanthanide derivatives in organic synthesis.
Samarium ii iodide in organic synthesis aroop chandra january 10th, 20. Divalent samarium is known to reduce alkyl halides. Tsuneo imamoto, in comprehensive organic synthesis, 1991. Samariumii iodide smi 2 is a mild oneelectron reducing agent used for various reductive reactions of carbonyl compounds, organic halides, and electron deficient olefins. Samariumii iodide smi2, kagans reagent has been widely used to forge.
Samarium ii iodide smi 2 is a green solid composed of samarium and iodine, with a melting point of 520 c. When hmpa complexes with smi 2, it raises the homo energy level in the resulting complex and, in so doing, reduces the energy required for electron transfer to the. Domino epoxide ringopeningketyl olefin coupling reactions. Flowers, ii, troels skrydstrup 2010 published by the royal society of chemistry. When employed as a solution for organic synthesis, it is known as kagans reagent. Lewis samarium ii iodide baran group meeting 1232010 3 carbonyl alkenealkyne coupling r o smi o r smi. Application of aluminum triiodide in organic synthesis juan tian and dayong sang jingchu university of technology, jingmen, hubei 448000, china. Benzannulated pyrrolizidines and indolizidines by smi 2 induced cyclizations of indole derivatives.
Samarium iodide is a oneelectron reductant, and typically effects reduction through a series of electron transfer and proton transfer from protic solvent steps. Historically, the use of smi2 in organic synthesis has been focused on the construction of carbocycles and oxygencontaining motifs. A novel and efficient samarium iodidemediated synthesis. The molybdenumcatalysed reduction of nitrogen to ammonia is achieved under ambient conditions, using samarium ii diiodide in combination with either simple alcohols or water as the proton source. Since its introduction to organic synthesis by kagan in 1980, samarium diiodide smi2, kagans reagent has, arguably, become the most. Samarium ii iodide is a powerful reducing agent for example it rapidly. First used in organic chemistry by kagan and coworkers in 1977,1 samarium diiodide. Chapter 20 reactions of samariumii iodide with carbohydrate. Samarium iodide is an inorganic compound with the formula smi2. Application of samarium reagents in organic synthesis. Lecture 3 applications of lanthanides reagent in organic.
It can be formed by high temperature decomposition of smi 3 the more stable iodide, but a convenient lab preparation is to react sm powder with 1,2diiodoethane in anhydrous thf, or ch 2 i 2 may also be used. The mechanistic role of hmpa and niii salts in the samarium barbier reaction. Samariumiimediated reactions in organic synthesis method development and mechanistic investigation tobias ankner department of chemistry university of gothenburg 2010 doctoral thesis submitted for partial fulfillment of the requirements for the degree of doctor in philosophy. Chiral 4substituted 2oxazolidinones and 5,5disubstituted oxazolidinones through asymmetric reformatsky type reaction. Please request a quote above to receive pricing information based on your specifications. Divalent lanthanide derivatives in organic synthesis. Organic synthesis using samarium diiodide rsc publishing. We report a short convenient total synthesis of csub 10 desmethyl arteannuin b utilizing an asymmetric reductive cyclization with samarium ii iodide which selectively forms the cisdecalin ring structure while setting the trans relationship between the subunits of the gammahydroxy ester. Mild preparation of samarium iodide and ytterbium iodide. Apr 24, 2019 the molybdenumcatalysed reduction of nitrogen to ammonia is achieved under ambient conditions, using samarium ii diiodide in combination with either simple alcohols or water as the proton source. Recent applications of kagans reagent smi 2 in natural product. Samariumiiiodidemediated cyclizations in natural product. The journal of organic chemistry 1997, 62 9, 29352943. Free electronic version of printed organic syntheses series detailed reliable experimental methods for the synthesis of organic compounds.
Samarium oxide is a catalyst for the dehydration and dehydrogenation of ethanol. Samariumii induced asymmetric reductive cyclizations. Twentyfive years of organic chemistry with diiodosamarium. The molybdenumcatalysed reduction of nitrogen to ammonia is achieved under ambient conditions, using samarium ii diiodide in combination with either simple alcohols or.
Troels skrydstrup is professor of organic chemistry at the university of aarhus, denmark and has years experience as an independent academic. Samarium diiodidemediated reactions in total synthesis. Thus, iodide 10 underwent a smi2promoted barbier cyclization to give. Samarium iodide interesting organic chemistry and natural. Organic synthesis using samarium diiodide request pdf. Reduction of anthracene and stilbene by samariumii iodidewater complex. Reviews and accounts arkivoc 2015 vi 446493 page 446 arkatusa, inc. Samarium diiodide smi2 is a oneelectron reducing agent that is employed extensively in organic synthesis to bring about a wide variety of transformations. Mild preparation of samarium iodide and ytterbium iodide and their use as reducing or coupling agents. However the killer step in sorensens route is the completely non selective oxidation of a methyl group with lead tetraacetatediacetoxyiodobenzene. Reductions with samariumii iodide organic reactions wiki.