Epoxidations sodium periodate

Alternatively, the cyclobutanones can be made by two-step procedures, i.e. osmium(VIII) oxide oxidation to the diol followed by further oxidation either by lead(IV) acetate 85 or sodium periodate,86,87 or epoxidation followed by oxidation with periodic acid,15,63 are reported to yield the ketones. 

On the pages which follow, general methods are illustrated for the synthesis of a wide variety of classes of organic compounds including acyl isocyanates (from amides and oxalyl chloride p. 16), epoxides (from reductive coupling of aromatic aldehydes by hexamethylphosphorous triamide p. 31), a-fluoro acids (from 1-alkenes p. 37), 0-lactams (from olefins and chlorosulfonyl isocyanate p. 51), 1 y3,5-triketones (from dianions of 1,3-diketones and esters p. 57), sulfinate esters (from disulfides, alcohols, and lead tetraacetate p. 62), carboxylic acids (from carbonylation of alcohols or olefins via carbonium-ion intermediates p. 72), sulfoxides (from sulfides and sodium periodate p. 78), carbazoles... 

Cobalt- or manganese-substituted PW12O40 and SiWiiOj9Ru(OH2)5 catalyze the oxidation of paraffins such as cyclohexane and adamantane (320, 321) as well as the epoxidation of cyclohexene with ter/-butyl hydroperoxide, iodosylbenzene potassium persulfate, and sodium periodate (321, 322). The reactivity depends on the transition metals. In the case of epoxidation of cyclohexene with iodosylbenzene, the order of catalytic activity of PW] i(M)03 is M = Co > Mn > Cu > Fe, Cr. 

In the presence of excess bipyridyl, ruthenium trichloride is an effective catalyst for the selective epoxidation of alkenes by sodium periodate (equation 297). The epoxidation is syn and stereospecific for cis and trans alkenes.637... 

End and Pfalz have reported that chiral ruthenium-bisamide (26) complex is a useful catalyst for epoxidation of E-olefins with sodium periodate as a terminal oxidant, although enantiose-lectivity is moderate (Scheme 6B.25) [70]. It is noteworthy that tranT-(I-mcthylstyrene is a better substrate than m-P-methylstyrene for this reaction in terms of enantioselectivity. Competitive... 

The use of cyclic sulfates in synthetic applications has been limited in the past because, although cyclic sulfites are easily prepared from diols, a convenient method for oxidation of the cyclic sulfites to cyclic sulfates had not been developed. The experiments of Denmark [70] and of Lowe and co-workers [71 ] with stoichiometric ruthenium tetroxide oxidations and of Brandes and Katzenellenbogen [72a] and Gao and Sharpless [68] with catalytic ruthenium tetroxide and sodium periodate as cooxidant have led to an efficient method for this oxidation step. Examples of the conversion of several diols (67) to cyclic sulfites (68) followed by oxidation to cyclic sulfates (69) are listed in Table 6D.7. The cyclic sulfite/cyclic sulfate sequence has been applied to 1,2-, 1,3-, and 1,4-diols with equal success. Cyclic sulfates, like epoxides, are excellent electrophiles and, as a consequence of their stereoelectronic makeup, are less susceptible to the elimination reactions that usually accompany attack by nucleophiles at a secondary carbon. With the development of convenient methods for their syntheses, the reactions of cyclic sulfates have been explored, Most of the reactions have been nucleophilic displacements with opening of the cyclic sulfate ring. The variety of nucleophiles used in this way is already extensive and includes H [68], [68,73-76], F" [68,72,74], PhCOCT [68,73,74], NOJ [68], SCN [68],... 

Alkenes may be epoxidized in an efficient manner by the use of tetrabutylammo-nium periodate, catalyzed by a manganese porphyrin63 in the presence of imidazole (equation 1)M. Sodium periodate may also be used as oxidant in a similar system65. 

The most widely used method for the preparation of 1,3,2-dioxathiolane. Y-oxides (cyclic sulfites) 65 bearing C-linked substituents is the reaction of the corresponding 1,2-diols with thionyl chloride in presence of pyridine or Et3N (Scheme 18). More reactive 1,3,2-dioxathiolane. Y,.Y-dioxidcs (cyclic sulfates) 66 are usually obtained by oxidation of sulfites 65 with sodium periodate, which is mediated by mthenium tetroxide generated in situ from a catalytic amount of ruthenium trichloride. Numerous derivatives 65 and 66 were obtained via this approach and its modifications for further transformations, mostly as the synthetic equivalents of epoxides <1997AHC89, 2000T7051> (see also Sections 6.05.5 and 6.05.6, and Tables 1-7). 

Epoxidation. Epoxidation of olefins with sodium periodate, using catalytic amounts of ruthenium(III) and employing (S)-(—)-4-(2-methylpropyl)-2-(2-pyridyl)-2-oxazoline as the chiral ligand (L ) for the metal, afforded products in 44-50% yield and enantioselectivities of 11-15% (eqs 3 and 4). ... 

The epoxidation procedures described here are not general ones they are used in special cases to prepare stereoisomers that are difficult to obtain by other means. 2,4-Disubstituted-6-hydroxymethylphenols have been oxidized with good yields to spirooxirane derivatives with sodium periodate in the case of bulky substituents, for example, when R = R = ferf-butyl (Eq. 47). ... 

Starting with geraniol (126), Sharpless asymmetric epoxidation [68] proceeded in 95% yield and with 93% ee (see Scheme 29) [69]. Hydrobromination of the alkene was achieved under standard conditions using NBS in THF and water (5 1) to afford a 64% yield of diastereomeric bromo alcohols (127). Cyclization to the tetrahydropyran diol was accomplished by treating 127 with camphorsulphonic acid in diethyl ether, followed by diol cleavage with sodium periodate to give a mixture of aldehydes 128 and 129. Upon... 

Mohajer, D., Tayebee, R., Goudarziafshar, H. Sodium Periodate Epoxidation of Aikenes Catalyzed by Manganese Porphyrins. J. Chem. Res., Synop. 1999, 168-169. 

B. Bahramian, V. Mirkhani, M. Moghadam, S. Tangestaninejad, Selective alkene epoxidation and alkane hydroxylation with sodium periodate catalyzed by cationic Mn(lll)-salen supported on Dowex MSCl, Appl. Catal. A 301 (2006) 169. 

Benzyl phenyl sulphide, norbornene, cw-cyclooctene, and 4-vinyl-1-cyclohexene were obtained from Aldrich and (IS)-(-)-a-pinene from Fluka. Phenyl sulphide was prepared from benzene and sulphur chloride following the literature procedure[9]. Reference samples of sulphoxides and sulphones were prepared by oxidation of sulphides with sodium periodate[10] and hydrogen peroxide[ll] respectively. Reference samples of epoxides were made by following Kaneda et al.[ 2 procedure. Metal phthalocyanines[13] were prepared from appropriate metal salt, 1,2-dicyanobenzene with ammonium molybdate as catalyst and were characterized by elemental analysis. 

Furthermore, pyrazol-3-ones have been oxidized by a variety of oxidizing agents such as ozone in oxygen, hydrogen peroxide solution, 3-chloroperbenzoic acid, aqueous sodium periodate, lead(IV) acetate with boron trifluoride etherate, or atmospheric oxidation. The reactions lead mainly to epoxidation of an alkene or imine functionality and cleavage of the pyrazol-3-one ring. 

Whilst the Sharpless epoxidation with titanium catalysts and the Jacobsen-Katsuki epoxidation with manganese(salen) complexes are at the forefront of enantioselec-tive epoxidation with metal catalysts, there are alternative systems available. Ruthenium pyridinebisoxazoline (PYBOX) complexes have been independently reported, using either phenyliodinium diacetate or sodium periodate as... 

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