Raney nickel epoxides

The zwitterion (6) can react with protic solvents to produce a variety of products. Reaction with water yields a transient hydroperoxy alcohol (10) that can dehydrate to a carboxyUc acid or spHt out H2O2 to form a carbonyl compound (aldehyde or ketone, R2CO). In alcohoHc media, the product is an isolable hydroperoxy ether (11) that can be hydrolyzed or reduced (with (CH O) or (CH2)2S) to a carbonyl compound. Reductive amination of (11) over Raney nickel produces amides and amines (64). Reaction of the zwitterion with a carboxyUc acid to form a hydroperoxy ester (12) is commercially important because it can be oxidized to other acids, RCOOH and R COOH. Reaction of zwitterion with HCN produces a-hydroxy nitriles that can be hydrolyzed to a-hydroxy carboxyUc acids. Carboxylates are obtained with H2O2/OH (65). The zwitterion can be reduced during the course of the reaction by tetracyanoethylene to produce its epoxide (66). 

Hydrogenation of 11,12a- epoxides over Raney nickel produces the 1 la-alcohol in 15-20% yield.The corresponding ll,12jS-epoxide gives the 12)5-carbinol, while cleavage of the 5,6a-epoxide gives the 5a-hydroxy compound and the 5,6)8- and 4,5)8-epoxides give mixtures of products. 

Some interesting results have been obtained from studies on the cleavage of 8,14-epoxides such as (65). In the presence of a A -double bond this epoxide is readily hydrogenolyzed over palladium. In the absence of this olefin, platinum and Raney nickel regenerate the A -olefin. ... 

The azidohydrins obtained by azide ion opening of epoxides, except for those possessing a tertiary hydroxy group, can be readily converted to azido mesylates on treatment with pyridine/methanesulfonyl chloride. Reduction and subsequent aziridine formation results upon reaction with hydrazine/ Raney nickel, lithium aluminum hydride, or sodium borohydride/cobalt(II)... 

Both regio- and stereospecificiiy may be influenced by the catalyst and by alkali. Raney nickel opens ce>2,3-diphenylbul-2-ene epoxide with retention of configuration to give cr3 f/iro-2,3-diphenylbutan-2-ol, whereas palladium-on-carbon gives the inverted threo isomer. If a small amount of alkali is added to nickel-catalyzed reductions, nickel too gives the threo isomer (d5). 

A novel approach to the synthesis of desoxy sugars was made by Jeanloz, Prins and Reichstein69 in 1945. In general terms, a 1,2-epoxide was cleaved with sodium thiomethoxide to give a /3-hydroxy thioether which, in turn, was hydrogenolyzed with Raney nickel. It is apparent... 

Prins64 has recently discovered that lithium aluminum hydride hydrogenates 1,2-epoxides smoothly in high yield this single-step reaction would appear to outmode the Raney nickel desulfurization process for this purpose. 

Cyclododecene may be prepared from 1,5,9-cyclododecatriene by the catalytic reduction with Raney nickel and hydrogen diluted with nitrogen, with nickel sulfide on alumina, with cobalt, iron, or nickel in the presence of thiophene, with palladium on charcoal, with palladimn chloride in the presence of water, with palladium on barium sulfate, with cobalt acetate in the presence of cobalt carbonyl, and with cobalt carbonyl and tri- -butyl phosphine. It may also be obtained from the triene by reduction with lithium and ethylamine, by disproportionation, - by epoxidation followed by isomerization to a ketone and WoliT-Kishner reduction, and from cyclododecanone by the reaction of its hydrazone with sodium hydride. ... 

In bromohydrins, hydrogenation over Raney nickel may lead to epoxides rather than to alcohols since regular Raney nickel contains enough alkali to cause dehydrobromination. Pure hydrogenolysis of bromine can be achieved over Raney nickel which has been washed free of alkah by acetic acid [631]. 

Open-chain aliphatic ethers are completely resistant to hydrogenolysis. Cyclic ethers (for epoxides, see p. 83) may undergo reductive cleavage under strenuous conditions. The tetrahydrofuran ring was cleaved in vigorous hydrogenations over Raney nickel [420] and copper chromite [420] to give, ultimately, alcohols. 

The racemic polyzonimine (19) is prepared as shown in Scheme 33. The expoxide (314) is rearranged to the aldehyde (315) by refluxing with LiBr-HMPA in benzene. Morpholine enamine (316) derived from 315 is condensed with nitroethylene, generated in situ from 2-acetoxynitroethane, to afford the nitroaldehyde (317). Ethylene acetalization, reduction over Raney nickel, and subsequent deacetalization give ( )-polyzonimine (19) in 22% overall yield from the epoxide (314) 113). 

Dimethyl-7-methoxyoctan-2-ol is prepared by hydrochlorination of dihy-dromyrcene, methoxylation of the resulting 2-chloro-2,6-dimethyl-7-octene and epoxidation. The alcohol is obtained by hydrogenation of the epoxide in the presence of Raney nickel and triethylamine [53]. It is used in perfumery as a top note in high quality sandalwood compositions for cosmetics, toiletries, and soaps. 

Among other reactions, the synthesis of the epoxide-N-oxide from retronecine should be mentioned82 the epoxide yields rosmarinecine on hydrogenation over Raney nickel (see Section III, A). The epoxy group has been recently demonstrated to be a constituent of certain... 

Hydrogenolysis of epoxides. Hydrogenation of the A -14a,l5a epoxide 1 over Raney nickel results in the desired alcohol 2 and the hydroxyl-free olefin 3 in about... 

EPOXIDES Alumina. r-Butyldimethyl-iodosilane. n-Butyllithium-Magnesium bromide. Cyclohexylisopropylamino-magnesium bromide. Dialkylaluminum amides. lodotrimethylsilane. Lithium l-a,a -dimethyldibenzylamide. Nafion-H. Organoaluminum compounds. Pyri-dinium chloride. Raney nickel. Tti-fluoroacetyl chloride, lrimethylsilyl-acctonitrile. Tris(phenylscleno)borane. Zinc iodide. 

In this synthesis the geometry of the acyclic double bonds is controlled through their formation as part of the thiane ring. Thiacyclohexanone (711) was converted to 4-thia-l-methylcyclohexene by reaction with methylmagnesium iodide and subsequent dehydration. Metallation of (712) with s-butyllithium and alkylation of the anion with the epoxide (713) gave a tertiary alcohol which was dehydrated to yield (714). A second alkylation of (714) with trails-4-chloro-3-methyl-2-butene 1-oxide (715) completed the carbon skeleton of the Cis juvenile hormone. Reduction of (716) with lithium in ethylamine and then desulfurization with Raney nickel led to trienol (717), a product converted previously to (718). 

The dithiane derivative 60 (Scheme 14) is such a compound, it being made from 2,3 5,6-di-0-isopropylidene-D-mannose by treatment with 2-lithio-l,3-dithiane to give a heptose dithioacetal that was refunctionalized at C-2-C-3 by way of the C-l anion and then converted to the 6,7-epoxide following selective acid-catalyzed cleavage of the 6,7-acetal ring. Treated with n-butyllithium it gives, in 70% yield, the cyclized 61, which is efficiently convertible into validatol 62, a component of validamycin A, by desulfurization with Raney nickel and de-O-protection by use of boron tribromide in dichloromethane [31]. 

Many other uses of a-sulfinyl carbanions are found in the literature, and in the recent past the trend has been to take advantage of the chirality of the sulfoxide group in asymmetric synthesis. Various ways of preparation of enantiopure sulfoxides have been devised (see Section 2.6.2) the carbanions derived from these compounds were added to carbonyl compounds, nitriles, imines or Michael acceptors to yield, ultimately, with high e.e. values, optically active alcohols, amines, ethers, epoxides, lactones, after elimination at an appropriate stage of the sulfoxide group. Such an elimination could be achieved by pyrolysis, Raney nickel or nickel boride desulfurization, reduction, or displacement of the C-S bond, as in the lactone synthesis reported by Casey [388]. 

Arene(tricarbonyl)chromium complexes, 19 Nickel boride, 197 to trans-alkenes Chromium(II) sulfate, 84 of anhydrides to lactones Tetrachlorotris[bis(l,4-diphenyl-phosphine)butane]diruthenium, 288 of aromatic rings Palladium catalysts, 230 Raney nickel, 265 Sodium borohydride-1,3-Dicyano-benzene, 279 of aryl halides to arenes Palladium on carbon, 230 of benzyl ethers to alcohols Palladium catalysts, 230 of carboxylic acids to aldehydes Vilsmeier reagent, 341 of epoxides to alcohols Samarium(II) iodide, 270 Sodium hydride-Sodium /-amyloxide-Nickel(II) chloride, 281 Sodium hydride-Sodium /-amyloxide-Zinc chloride, 281 of esters to alcohols Sodium borohydride, 278 of imines and related compounds Arene(tricarbonyl)chromium complexes, 19... 

All types of electrophiles have been used with 2-lithio-l,3-dithiane derivatives, including alkyl halides, sulfonates, sulfates, allylic alcohols, arene-metal complexes, epoxides, aziridines, carbonyl compounds, imines, Michael-acceptors, carbon dioxide, acyl chlorides, esters and lactones, amides, nitriles, isocyanates, disulfides and chlorotrialkylsilanes or stannanes. The final deprotection of the dithioacetal moiety can be carried out by means of different types of reagents in order to regenerate the carbonyl group by heavy metal coordination, alkylation and oxidation184 or it can be reduced to a methylene group with Raney-nickel, sodium or LiAIII4. 

Epoxide cleavage, Sodium selenophenolate reacts with the furanose 1, prepared from D-glucose, to form the diselenide 3 in quantitative yield. This reaction involves formation and cleavage of the epoxide 2, which can be also prepared by treatment of 1 with NaH. The epoxide is cleaved regiospecifically by attack from the less hindered side at C4. The phenylseleno group can be removed reductively by Raney nickel. The product was used to prepare isoepiallomuscarine (5). 

Synthesis of P-Keto Sulfoxides. Optically active p-keto sulfoxides are very useful building blocks (eq 4) because they can be stereoselectively reduced to afford either diastereomer of the corresponding p-hydroxy sulfoxide under appropriate conditions (Diisobutylaluminum Hydride or Zinc ChloridefDlBALf and thus give access to a wide variety of compounds chiral carbinols by desulfurization with Raney Nickel or LithiumJethyhmme ini the case of allylic alcohols epoxides via cyclization of the derived sulfonium salt butenolides by alkylation of the hydroxy sulfoxide 1,2-diols via a Pummerer rearrangement followed by reduction of the intermediate. ... 

Table 10 Raney-Nickel Catalyzed Hydrogenolysis of Epoxides...

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