Oxidation reactions Samarium iodide

Barbier reaction Samarium(II) iodide, 270 Benzoannelation Chromium carbene complexes, 82 Dicarbonylcyclopentadienylcobalt, 96 Ethyl (Z)-3-bromoacryIate, 130 Grignard reagents, 138 Methyl acrylate, 183 Methyllithium, 188 Ruthenium(III) chloride, 268 Benzoin condensation Benzyltriethylammonium chloride, 239 3-EthyIbenzothiazolium bromide, 130 Benzoylation (see also Acylation) Cadmium, 60 Dibutyltin oxide, 95 Birch reduction Birch reduction, 32... 

Norephedrine, 200 Organoaluminum reagents, 202 Organotitanium reagents, 213 9-(Phenylseleno)-9-borabicyclo-[3.3.1]nonane, 245 Tin(II) chloride, 298 Titanium(IV) chloride, 304 Trityllithium, 338 Trityl perchlorate, 339 Zinc chloride, 349 By other reactions Chloromethyl ethyl ether, 75 Dibutyltin oxide, 95 Samarium(II) iodide, 270 Tributyltin hydride, 316 Hydroxy amides a-Hydroxy amides... 

Finally, it can be stated that many reactivity patterns of free radical ions are equally found in oxidative and reductive transformations involving initial inner-sphere ET, such as in reactions with samarium iodide [389], low valent titanium [390] and titanocene complexes [391], manganese(III) [392], and CAN [393]. 

The reaction of ketones 107 with [hydroxy(4-nitrobenzenesulfonyloxy)iodo]benzene and subsequent treatment with samarium iodide has been used for a one-pot preparation of a-iodoketones 108 (Scheme 3.43) in high yields [118]. 2-Iodosylbenzoic acid can also be used as a convenient recyclable hypervalent iodine oxidant for the synthesis of a-iodoketones by oxidative iodination of ketones [119]. 

This reaction has been modified to different variants, including the initiation from fluoride, cuprous ion, samarium iodide, and oxidative electron transfer and the cleavage of acetonide, -tributylstannyl alcohol, and different ether protecting groups. 

The synthesis of sphingosine from 2,4- -benzylidene-E>-threose was hampered by ftilure to achieve ara /no-selectivity in the addition of tetradecosylmagnesium bromide as well as in the oxidation/reduction of the resulting mixed alcohols by all methods tried except the samarium iodide-assisted Tishchenko reaction. ... 

The projected free radical cyclization proceeded as planned to give 172. Ozonolysis of the vinyl group, oxidation of the resulting aldehyde to an acid, and alkylation with diazomethane provided projected intermediate 162. Reduction of the lactone provided 173. Treatment of 173 with 6-methoxytryptamine and pivalic acid then provided a nearly equal mixture of lactams 174 (isoreserpine stereochemistry at Cg) and 175 (reserpine stereochemistry at C3). The correct C3 stereoisomer was moved forward to 176 (protection of the tertiary alcohol followed by reduction of the lactam). The silyl ethers were removed, the secondary ether was re-protected, and reaction with samarium iodide accomplished reduction of the a-hydroxy ester to provide 177. Removal of the TBS group and esterification of the alcohol completed the synthesis of reserpine. 

Samarium(II) iodide, 46, 3 Sandmeyer reaction, 2, 7 Schiemann reaction, 5, 4 Schmidt reaction, 3, 8, 9 Selenium dioxide oxidation, 5, 8 24, 4 Seleno-Pummerer reaction, 40, 3 Selenoxide elimination, 44, 1 Shapiro reaction, 23, 3 39, 1 Silanes ... 

Using chromium-based oxidants 2,4-Dimethylpentane-2,4-diol chromate(VI) diester, 122 Trimethylsilyl chlorochromate, 327 Using other oxidizing agents Bis(tributyltin) oxide, 41 Hydrogen hexachloroplatinate(IV)-Copper(II) chloride, 145 4-Methoxy-2,2,6,6-tetramethyl-1 -oxopiperidinium chloride, 183 Osmium tetroxide, 222 Potassium nitrosodisulfonate, 258 Samarium(II) iodide, 270 From alkenes by addition or cleavage reactions... 

Chiral induction was also observed in lanthanide(III)-alkoxide-mediated MPV reductions. The optically active ligand (Fig. 35C) was used in enantioselec-tive samarium-catalyzed MPV reductions of arylmethyl ketones (Scheme 30) [253], The resulting mixed alkoxide-iodide complex shows higher reactivity than (rBuO)SmI2. It was pointed out that the tridentate, secondary alkoxide ligand is not oxidized under the reaction conditions and that tridendate ligands... 

Since the intramolecular reactions are so much the best, others have linked the alkene and the alkyne by a weak bond that can later be sacrificed. This is the tether strategy you will meet in chapter 36. An N-0 bond is ideal and with the alkyne additionally blocked with a silyl group 124, good yields of Pauson-Khand product 125 and of the amino alcohol 126 could be achieved even with an amine A-oxide as promoter. Samarium(II) iodide was used as the reducing agent.35... 

Grignard type compounds of some lanthanide metals in the oxidation state +2 have been investigated by D.F. Evans et al. (1970, 1971). Europium, samarium and ytterbium react in tetrahydrofuran with alkyl and aryl iodides between —20 and + 30°C forming colored solutions containing mixtures of compounds, which give some Grignard-type reactions. Characterization of the compounds was done only by magnetic susceptibility measurements and some titrimetric analyses. 

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