Recent applications of kagans reagent smi 2 in natural product. Samarium ii iodide in organic synthesis aroop chandra january 10th, 20. Troels skrydstrup is professor of organic chemistry at the university of aarhus, denmark and has years experience as an independent academic. 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. Smi2 is a green solid and its solutions are green as well. Samarium diiodidemediated reactions in total synthesis ncbi.
Chiral 4substituted 2oxazolidinones and 5,5disubstituted oxazolidinones through asymmetric reformatsky type reaction. Tsuneo imamoto, in comprehensive organic synthesis, 1991. Preparation and use of samarium diiodide smi 2 in organic synthesis. Samariumiimediated reactions in organic synthesis method. Synthesis of nitrogen heterocycles using samariumii iodide mdpi. Reduction of anthracene and stilbene by samariumii iodidewater complex. Benzannulated pyrrolizidines and indolizidines by smi 2 induced cyclizations of indole derivatives. Psd were measured using sigma scan pro software jandel scientific. First used in organic chemistry by kagan and coworkers in 1977,1 samarium diiodide. Smi 2 is a green solid and its solutions are green as well. Thus, iodide 10 underwent a smi2promoted barbier cyclization to give.
The molybdenumcatalysed reduction of nitrogen to ammonia is achieved under ambient conditions, using samarium ii diiodide in combination with either simple alcohols or. Protonation accepting a proton from a suitable donor is a characteristic reaction of an organosamarium compound. Introduction and backgroundintramolecular barbier reactionintramolecular reformatsky reactionradical alkene and alkyne cyclizationscarbonylalkene reductive cyclizations. Samariumii iodide mediated cyclizations in natural product. 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. In 1979, kagan observed the reduction of a variety of organic functional groups by samarium iodide under mild conditions. Reviews and accounts arkivoc 2015 vi 446493 page 446 arkatusa, inc. Since its introduction to organic synthesis by kagan in 1980, samarium diiodide smi2, kagans reagent has, arguably, become the most. Samariumii iodide mediated cyclizations in natural product synthesis the kagan reagent part ii an evans group afternoon seminar keith fandrick seminar outline. Flowers, ii, troels skrydstrup 2010 published by the royal society of chemistry. 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. 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.
Mild preparation of samarium iodide and ytterbium iodide. Samariumii iodide mediated intramolecular aldoltype. Every effort has been made to ensure the accuracy of the organic iodide powder information published above. Search results for samarium iodide at sigmaaldrich. Samariumii iodide smi 2 is a mild oneelectron reducing agentused for various reductive reactions of carbonyl compounds, organic halides, and electron deficient olefins. Benzannulated pyrrolizidines and indolizidines by smi 2induced cyclizations of indole derivatives. Chapter 20 reactions of samariumii iodide with carbohydrate. Samariumii iodide is an inorganic compound with the formula smi2. Lecture 3 applications of lanthanides reagent in organic. Preparation and use of samarium diiodide smi2 in organic. 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.
Organic synthesis using samarium diiodide rsc publishing. Reactions of samariumii iodide with carbohydrate derivatives 470 iv. Samarium oxide is a catalyst for the dehydration and dehydrogenation of ethanol. Samarium ii iodide solution smi 2 can be used as a reagent in the synthesis of. 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. The journal of organic chemistry 1997, 62 9, 29352943. The mechanistic role of hmpa and niii salts in the samarium barbier reaction. 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. Application of aluminum triiodide in organic synthesis juan tian and dayong sang jingchu university of technology, jingmen, hubei 448000, china. 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. The journal of organic chemistry 2014, 79 6, 25222537.
His research interests lie in the development of organic reactions and their. Enantioselective cyclizations and cyclization cascades of. Samarium ii iodide solution is available in standard form as a 0. When employed as a solution for organic synthesis, it. It is a strong oneelectron reducing agent that is used in organic synthesis. The paterson synthesis does not have such a nonselective step but still requires 6 equivalents of samarium iodide, why are 6 equivalents necessary. Samariumii induced asymmetric reductive cyclizations. Please request a quote above to receive pricing information based on your specifications. Samarium ii iodide is a powerful reducing agent for example it rapidly. Full text of samarium diiodide reactions of alphaoxygenated. Samariumii iodide solution smi 2 can be used as a reagent in the synthesis of.
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. Samarium ii iodide is used as a chemical reagent in organic synthesis, for example in the barbier reaction. Mild preparation of samarium iodide and ytterbium iodide and their use. Organic preparations and procedures international 2003, 35 3, 307360. Samarium iodide is a oneelectron reductant, and typically effects reduction through a series of electron transfer and proton transfer from protic solvent steps. Samarium iodide interesting organic chemistry and natural. 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. Synthesis of nitrogen heterocycles using samarium ii iodide. Feb 04, 20 divalent lanthanide derivatives in organic synthesis. Divalent lanthanide derivatives in organic synthesis. A novel and efficient samarium iodidemediated synthesis. Samariumiiiodidemediated cyclizations in natural product. Applications of samarium iodide reagent to reduce alkyl halide to alkane,ketones and aldheydes to alcohols with complete explaination by various examples. Smi2 is a versatile reagent now widely used in organic chemistry.
Samarium iodide is an inorganic compound with the formula smi2. However, it remains the responsibility of the readers to familiarize themselves with the product information contained on the us product label or package insert. 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. Additional applications of smi 2 include pinalol coupling, alkylcarbonyl coupling, deoxygenation, the reformatsky reaction, and freeradical mediated cyclization. Twentyfive years of organic chemistry with diiodosamarium. Samariumii iodide smi2, kagans reagent has been widely used to forge. Samarium diiodidemediated reactions in total synthesis. Reductions with samariumii iodide organic reactions wiki. Structure, properties, spectra, suppliers and links for. Lewis samarium ii iodide baran group meeting 1232010 3 carbonyl alkenealkyne coupling r o smi o r smi. Domino epoxide ringopeningketyl olefin coupling reactions. However the killer step in sorensens route is the completely non selective oxidation of a methyl group with lead tetraacetatediacetoxyiodobenzene. Samariumii iodide smi 2 is a green solid composed of samarium and iodine, with a melting point of 520 c. Historically, the use of smi2 in organic synthesis has been focused on the.
Samariumii iodide smi 2 is a mild oneelectron reducing agent used for various reductive reactions of carbonyl compounds, organic halides, and electron deficient olefins. A novel and efficient samarium iodidemediated synthesis of. 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. Financial support of our program by rutgers university is gratefully acknowledged. But when combined with hmpa, samarium iodide is also capable of bringing about. 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. Free electronic version of printed organic syntheses series detailed reliable experimental methods for the synthesis of organic compounds. 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. Recent studies on samarium diiodide mediated organic synthesis. Application of aluminum triiodide in organic synthesis. Samariumii iodide is an inorganic compound with the formula smi 2.
Full text of samarium diiodide reactions of alphaoxygenated carbonyls see other formats samarium diiodide reactions of alpha oxygenated carbonyls by jeffrey a. Preparation and use of samarium diiodide smi2 in organic synthesis. Divalent samarium is known to reduce alkyl halides. Molybdenumcatalysed ammonia production with samarium.
When employed as a solution for organic synthesis, it is known as kagans reagent. Fabrice denes, mark pichowicz, guillaume povie, and philippe renaud. Historically, the use of smi2 in organic synthesis has been focused on the construction of carbocycles and oxygencontaining motifs. 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. Crosscoupling reactions using samariumii iodide chemical. Mild preparation of samarium iodide and ytterbium iodide and their use as reducing or coupling agents. Although samarium diiodide is used extensively by organic chemists, there is still a widely held view that the reagent can be difficult to prepare and use. Application of samarium reagents 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. Samarium compounds act as sensitizers for phosphors excited in the infrared. The mechanistic role of hmpa and niii salts in the samarium barbier. Organic synthesis using samarium diiodide request pdf.
Samarium ii iodide smi 2 is a green solid composed of samarium and iodine, with a melting point of 520 c. Samarium oxide is used in optical glass to absorb infrared light. Samarium diiodide smi2 is a oneelectron reducing agent that is employed extensively in organic synthesis to bring about a wide variety of transformations. When employed as a solution for organic synthesis, it is. Organic synthesis using samarium diiodide a practical guide.