Reductive iodinations using

Reduction to Halocarbons. The best conditions for the reductive chlorination of ketones use the reagent combination Me2ClSiH/In(OH)3 (Eq. 241).331 Examples include conversions of aryl ketones to benzyl chlorides, ethynyl ketones to propargyl chlorides, and alkyl ketones to alkyl chlorides (Eq. 242).331 Addition of lithium iodide to the reaction mixture yields the corresponding iodide product. The combination of TMDO/I2 reductively iodinates aryl ketones and aldehydes in good yields (Eq. 243).357... 

SASD (Chapter 5, Section 3.2) behaves in a similar manner, except it contains an amine-reactive end that can be coupled to proteins and other molecules. Its photoreactive end can be iodinated using any of the radioiodination reagents discussed previously. Just as in the case of APDP, SASD cross-links can be cleaved by a disulfide reductant to transfer the radioactive component to a second molecule. 

Among the more unusual modes of epoxide reactivity is a technique for reductive deoxygenation using a system of triphenylphosphine and iodine in dimethylformamide (DMF). Under these conditions, the functionalized epoxide 98 was quantitatively converted to the diallyl ether 99. Similar conditions were found to convert epoxides to the interestingly substituted (5-bromoformate derivatives (e.g. 101) <02T7037>. 

We have examined the applications of IBH2 and I2BH complexes for hydroboration of alkenes to obtain dialkyl and mono alkyl boranes. Unfortunately, these species disproportionate and hence the dialkyl and trialkyl boranes were not formed cleanly. Fortunately, however, the HBI2 and BI3 complexes are found to be useful for iodinations of alcohols, reductive iodinations of carbonyl compounds and hydroiodination of alkenes and alkynes. 

The dichromate ion oxidises iron(II) to iron(III), sulphite to sulphate ion, iodide ion to iodine and arsenic(III) to arsenic(V) (arsenate). Reduction of dichromate by sulphite can be used to prepare chrome alum, since, if sulphur dioxide is passed into potassium dichromate acidified with sulphuric acid, potassium and chromium(III) ions formed are in the correct ratio to form the alum, which appears on crystallisation ... 

With Phenylpropanolamine at hand (or ephedrine and pseudo-ephedrine) one would next need to reduce that alpha carbon OH group to get the final amine. Strike understands that the current favorite methods for doing this involve lithium and amine. HI and red P or other iodine related protocols. So when you meth heads ruin every aspect of those methods as well, what will you do then The following are a couple of OH reduction methods (Strike thinks) that have applicable use [99-100]. 

The majority of preparative methods which have been used for obtaining cyclopropane derivatives involve carbene addition to an olefmic bond, if acetylenes are used in the reaction, cyclopropenes are obtained. Heteroatom-substituted or vinyl cydopropanes come from alkenyl bromides or enol acetates (A. de Meijere, 1979 E. J. Corey, 1975 B E. Wenkert, 1970 A). The carbenes needed for cyclopropane syntheses can be obtained in situ by a-elimination of hydrogen halides with strong bases (R. Kdstcr, 1971 E.J. Corey, 1975 B), by copper catalyzed decomposition of diazo compounds (E. Wenkert, 1970 A S.D. Burke, 1979 N.J. Turro, 1966), or by reductive elimination of iodine from gem-diiodides (J. Nishimura, 1969 D. Wen-disch, 1971 J.M. Denis, 1972 H.E. Simmons, 1973 C. Girard, 1974),... 

Ofner Method. This method is for the determination of invert sugar in products with up to 10% invert in the presence of sucrose and is a copper-reduction method that uses Ofner s solution instead of Fehling s. The reduced cuprous oxide is treated with excess standardized iodine, which is black-titrated with thiosulfate using starch indicator. 

Sulfonic acids are prone to reduction with iodine [7553-56-2] in the presence of triphenylphosphine [603-35-0] to produce the corresponding iodides. This type of reduction is also facile with alkyl sulfonates (16). Aromatic sulfonic acids may also be reduced electrochemicaHy to give the parent arene. However, sulfonic acids, when reduced with iodine and phosphoms [7723-14-0] produce thiols (qv). Amination of sulfonates has also been reported, in which the carbon—sulfur bond is cleaved (17). Ortho-Hthiation of sulfonic acid lithium salts has proven to be a useful technique for organic syntheses, but has Httie commercial importance. Optically active sulfonates have been used in asymmetric syntheses to selectively O-alkylate alcohols and phenols, typically on a laboratory scale. Aromatic sulfonates are cleaved, ie, desulfonated, by uv radiation to give the parent aromatic compound and a coupling product of the aromatic compound, as shown, where Ar represents an aryl group (18). 

Ana.lytica.1 Methods. Various analytical methods involve titration with oxidants, eg, hexacyanoferrate (ferricyanide), which oxidize dithionites to sulfite. lodimetric titration to sulfate in the presence of formaldehyde enables dithionite to be distinguished from sulfite because aldehyde adducts of sulfite are not oxidized by iodine. Reductive bleaching of dyes can be used to determine dithionite, the extent of reduction being deterrnined photometrically. Methods for determining mixtures of dithionite, sulfite, and thiosulfates have been reviewed (365). Analysis of dithionite particularly for thiosulfate, a frequent and undesirable impurity, can be done easily by Hquid chromatography (366). 

A unique problem arises when reducing the fissile isotope The amount of that can be reduced is limited by its critical mass. In these cases, where the charge must be kept relatively small, calcium becomes the preferred reductant, and iodine is often used as a reaction booster. This method was introduced by Baker in 1946 (54). Researchers at Los Alamos National Laboratory have recently introduced a laser-initiated modification to this reduction process that offers several advantages (55). A carbon dioxide laser is used to initiate the reaction between UF and calcium metal. This new method does not requite induction heating in a closed bomb, nor does it utilize iodine as a booster. This promising technology has been demonstrated on a 200 g scale. 

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