Alkenes sodium periodate

C.U. Sodium Periodate In section 3.7.A.ii, a mixture of osmium tetroxide and periodic acid oxidatively cleaved alkenes. Sodium periodate can cleave diols directly. In the Chida et al. synthesis of pironetin, for example, 371 was cleaved to dialdehyde 372 using an aqueous acetone solution of NalOq. l Sodium periodate in dichloromethane, in the presence of sodium bicarbonate, has also been used.5l9... 

Osmium tetroxide used in combination with sodium periodate can also effect alkene cleavage.191 Successful oxidative cleavage of double bonds using ruthenium tetroxide and sodium periodate has also been reported.192 In these procedures the osmium or ruthenium can be used in substoichiometric amounts because the periodate reoxidizes the metal to the tetroxide state. Entries 1 to 4 in Scheme 12.18 are examples of these procedures. Entries 5 and 6 show reactions carried out in the course of multistep syntheses. The reaction in Entry 5 followed a 5-exo radical cyclization and served to excise an extraneous carbon. The reaction in Entry 6 followed introduction of the allyl group by enolate alkylation. The aldehyde group in the product was used to introduce an amino group by reductive alkylation (see Section 5.3.1.2). 

Oxidative cleavage of alkenes using sodium periodate proceeds effectively in a monophasic solution of acetic acid, water, and THF with very low osmium content or osmium-free. The orders of reactivity of alkenes are as follows monosubstituted trisubstituted >1,2 disub-stituted > 1,1-disubstituted > tetrasubstituted alkynes.100 Cleavage with polymer-supported OSO4 catalyst combined with NaI04 allows the reuse of the catalyst.101... 

In summary, the reaction of osmium tetroxide with alkenes is a reliable and selective transformation. Chiral diamines and cinchona alkakoid are most frequently used as chiral auxiliaries. Complexes derived from osmium tetroxide with diamines do not undergo catalytic turnover, whereas dihydroquinidine and dihydroquinine derivatives have been found to be very effective catalysts for the oxidation of a variety of alkenes. OsC>4 can be used catalytically in the presence of a secondary oxygen donor (e.g., H202, TBHP, A -methylmorpholine-/V-oxide, sodium periodate, 02, sodium hypochlorite, potassium ferricyanide). Furthermore, a remarkable rate enhancement occurs with the addition of a nucleophilic ligand such as pyridine or a tertiary amine. Table 4-11 lists the preferred chiral ligands for the dihydroxylation of a variety of olefins.61 Table 4-12 lists the recommended ligands for each class of olefins. 

In their pioneering work. Just and co-workers have described many interesting transformations of the Diels-Alder adducts of furan to methyl nitroacrylate (77 + 77 ) and to dimethyl acetylenedicarboxylate (53). The mixture of racemic adducts 77 + 77 was hydroxylated into the exo-cis-diols 125 + 125 , separable by crystallization. Treatment of the isopropylidene acetal obtained from 125 with diazabicyclo[5.4.0]undec-5-ene (DBU) gave a high yield of alkene 126. Ozonolysis followed by a reductive work-up with dimethylsulfide, then with NaBH4, gave a mixture of epimeric triols 127. Cleavage with sodium periodate afforded 2,5-anhydro-3,4-0-isopropylidene-DL-allose (128) in 15 % yield, based on methyl 2-nitroacrylate used. TTie same allose derivative was obtained from adduct 53. ... 

Osmium tetroxide used in combination with sodium periodate can also effect alkene cleavage.135 Successful oxidative cleavage of double bonds using ruthenium tetroxide and sodium periodate has also been reported.136 In these procedures, the osmium or ruthenium can be used in substoichiometric amounts because the periodate reoxidizes the metal to the tetroxide state. Entries 1 4 in Scheme 12.17 are examples of these procedures. 

Pure homoallylic alcohols are converted into y-amino-p-hydroxy acids by protection as the TBDMS ether or A(0-acetonide followed by degradative oxidation of the terminal alkene using a catalytic amount of ruthenium(III) chloride and sodium periodate (Scheme... 

Aldehydes and ketones often can be prepared by oxidation of alkenes to 1,2-diols (Sections 11-7C and 11-7D), followed by oxidative cleavage of the 1,2-diols with lead tetraethanoate or sodium periodate. For example,... 

Exercise 16-37 An elegant modification of the two-step procedure to prepare ketones from alkenes by hydroxylation and oxidative cleavage of the diol formed uses a small amount of potassium permanganate (or osmium tetroxide, 0s04) as the catalyst and sodium periodate as the oxidizing agent ... 

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... 

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... 

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. 

Two tandem alkene metathesis-oxidation procedures using Grubb s second-generation ruthenium catalyst resulted in unique functional group transformations. Use of sodium periodate and cerium(III) chloride, in acetonitrile-water, furnished cis-diols. Oxidation with Oxone, in the presence of sodium hydrogencarbonate, yielded a-hydroxy ketones.296 Secondary alcohols are oxidized to ketones by a hydrogen... 

Trithioles and 1,3,2-dioxathiolanes. 1,2,3-Trithiolanes are prepared by reaction of alkenes with elemental sulfur . The synthesis of 1,3,2-dioxathiolane -oxides (cyclic sulfites) and 1,3,2-dioxathiolane S, -dioxides (cyclic sulfates) is discussed in comprehensive reviews <1997AHC(68)89, 2000T7051>. The most widely used method for the preparation of 1,3,2-dioxathiolane A-oxides 557 is the reaction of the corresponding 1,2-diols 556 with thionyl chloride in the presence of pyridine or triethylamine (Scheme 251). More reactive 1,3,2-dioxathiolane S,A-dioxides 558 are usually obtained by oxidation of sulfites 557 with sodium periodate, which is mediated by ruthenium tetroxide generated in situ from a catalytic amount of ruthenium trichloride <1997AHC89, 2000T7051, CHEC-III(6.05.10.3)183>. 

Aldehydes, RCHO (Sec. 7.9) (Sec. 7.9) (Sec. 8.4) (Sec. 17.7, 19.2) (Sec. 19.2, 21.6) from disubstituted alkenes by ozonolysis from 1,2-diols by cleavage with sodium periodate from terminal alkynes by hydroboration followed by oxidation from primary alcohols by oxidation from esters by reduction with DIB AH [HA1(i-Bu)2]... 

Sodium periodate (sodium metaperiodate), NaI04 (mp 300 °C dec), which is commercially available, is applied mainly in aqueous or aqueous-alcoholic solutions. Like the free periodic acid, sodium periodate cleaves vicinal diols to carbonyl compounds [762], This reaction is especially useful in connection with potassium permanganate [763, 764] or osmium tetroxide [765], Such mixed oxidants oxidize alkenes to carbonyl compounds or carboxylic acids, evidently by way of vicinal diols as intermediates. Sulfides are transformed by sodium periodate into sulfoxides [322, 323, 766, 767, 768, 769, 770, 771, 772], and selenides are converted into selenoxides [773]. Sodium periodate is also a reoxidant of lower valency ruthenium in oxidations with ruthenium tetroxide [567, 774],... 

The results of some oxidations with potassium permanganate differ depending on the pH of the reaction. For example, stearolic acid gives 9,10-diketostearic acid at pH 7-7.5 (achieved with carbon dioxide) and azelaic acid on treatment at pH 12 [864]. In some reactions, potassium permanganate is used as a catalyst for oxidation with other oxidants, such as sodium periodate. Thus alkenes are cleaved to carbonyl compounds or acids via vicinal diols obtained by hydroxylation with potassium permanganate, followed by cleavage by sodium periodate [763, 552]. 

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... 

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. 

Gallc er and co-workers devised a formal enantioselective synthesis of ( — )-3 in wduch the stereogenic center at C-6 was derived fiom Cbz-protected (S)-2-amino-4-pentenoic acid (36) (44). Acylation of 3,3-dimethoxy-pyrrolidine (37) with this acid yielded amide 38, which was converted into aldehyde 39 by cleavage of the terminal alkene vnth osmium tetroxide and sodium periodate (Scheme 5). The indolizidine nucleus was constructed from 39 by a problematic intramolecular aldol condensation, which was eventually optimized by using 2,2,6,6-tetramethylpiperidine as base followed by adsorption onto, and elution from, silica gel (45). Diastereoselective reduction of the ketone group of the aldol product 40 was accomplished in better than 95% enantiomeric excess (ee) with the Corey... 

Oxidation of the hydroxymalonic acid ene adducts with cerium(IV) ammonium nitrate in aqueous acetonitrile or sodium periodate results in oxidative didecarboxylation to give an allylcarboxylic acid. The two step process ene reaction with diethyl oxomalonate and oxidative didecarboxylation provides a general procedure for the conversion of alkenes to allylcarboxylic acids. 

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. 

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