Nickel boride reduction

The chiral, reactive 2(3// )-quinazolinone 406 underwent diastereoselective reduction with lithium tri(fer7-butoxy)-aluminium hydride at —60°C to generate the 1,4-dihydro derivative 407 <2003JOC754>, while nickel boride reduction of the 2-thioxoquinazoline 408 gave the 2,3-dihydro-4(177)-quinazolinone 409 <2003JHG677>. 

Following nickel boride reduction, the disaccharide 199 results which by a similar treatment first with lithium iodide and then with methyl lithium gives the disaccharide glycal 200. Another glycosylation with 195 and NIS leads to the trisaccharide digi-toxose derivative 201 (53%) [105]. 

By far the most concise and efficient approach to ( + /—)-stemoamide (15) was developed by Jacobi and Lee (71,72) and featured an intramolecular Diels-Alder/retro Diels Alder cyeloaddition between the 2-methoxyoxazole and acetylenic moieties in 151 followed by equilibration to set the correct relative configuration at C8 and C9a (151 147, Scheme 11). The stereochemistry at C9 and CIO was established after nickel boride reduction of the unsaturated butyrolactone ring and epimerization at CIO to afford a 73% yield of ( + /—)-stemoamide (15), together with its epimer at C9 and CIO. Overall, the total synthesis of (+ /—)-stemoamide (15) was achieved in seven steps from 4-chlorobut5Tyl chloride (148) and in 20% overall yield. 

Reduction and desulfurization of hetarenes with participation of nickel boride 970PP1. 

Catalysts show remarkable product variation in hydrogenation of simple nitriles. Propionitrile, in neutral, nonreactive media, gives on hydrogenation over rhodium-on-carbon high yields of dipropylamine, whereas high yields of tripropylamine arise from palladium or platinum-catalyzed reductions (71). Parallel results were later found for butyronitrile (2S) and valeronitrile (74) but not for long-chain nitriles. Good yields of primary aliphatic amines can be obtained by use of cobalt, nickel, nickel boride, rhodium, or ruthenium in the presence of ammonia (4J 1,67,68,69). 

Nickel borides are usually prepared by reduction of nickel salts with sodium or potassium borohydride. Two types are used. PI nickel boride is prepared by the reaction between aqueous solutions of nickel salts and a borohy-... 

The reductive cleavage of the N-O bond in the isoxazolidine 162 unmasks the 1,3-amino alcohol moiety. Thus, isoxazolidines can be viewed as direct precursors of 7-amino alcohols. The reductive cleavage of the cycloadduct proved difficult. W2 Raney-Ni and nickel boride were both ineffective. In contrast, nickel-aliminium alloy in an alkaline medium efficiently reduced the N-O bond at room temperature in the presence of a base (Equation 27) <1997TA109>. 

Nickel of activity comparable to Raney nickel is obtained by reduction of nickel salts, e.g. nickel acetate, with 2 mol of sodium borohydride in an aqueous solution and by washing the precipitate with ethanol [13, 47] Procedure 7, p. 205). Such preparations are designated P-1 or P-2 and can be conveniently prepared in situ in a special apparatus [4] Procedure 2, p. 202). They contain a high percentage of nickel boride, are non-magnetic and non-pyrophoric and can be used for hydrogenations at room temperature and... 

Another highly active non-pyrophoric nickel catalyst is prepared by reduction of nickel acetate in tetrahydrofuran by sodium hydride at 45° in the presence of tert-amyl alcohol (which acts as an activator). Such catalysts, referred to as Nic catalysts, compare with P nickel boride and are suitable for hydrogenations at room temperature and atmospheric pressure, and for partial reduction of acetylenes to civ-alkenes [49]. 

Hydrogenation using Raney nickel is carried out under mild conditions and gives cis alkenes from internal alkynes in yields ranging from 50 to 100% [356, 357, 358, 359, 360]. Half hydrogenation of alkynes was also achieved over nickel prepared by reduction of nickel acetate with sodium borohydride (P-2 nickel, nickel boride) [349,361,362] or by reduction with sodium hydride [49], or by reduction of nickel bromide with potassium-graphite [363]. Other catalysts are palladium on charcoal [364], on barium sulfate [365, 366], on... 

Aliphatic and aromatic sulfides undergo desulfurization with Raney nickel [673], with nickel boride [673], with lithium aluminum hydride in the presence of cupric chloride [675], with titanium dichloride [676], and with triethyl phosphite [677]. In saccharides benzylthioethers were not desulfurized but reduced to toluene and mercaptodeoxysugars using sodium in liquid ammonia [678]. This reduction has general application and replaces catalytic hydrogenolysis, which cannot be used [637]. 

Nickel boride, formed in situ from sodium borohydride and nickel chloride, has been used to prepare dihydro derivatives from thiothymine 385 <2001JME1853> and thiobarbituric acid derivatives 388 <2002J(P1)2520>. With 4-thiothymine derivatives, an isomeric mixture of 3,4- and 3,6-dihydro derivatives 386 and 387 was obtained <2001JME1853>, but with 2-thiobarbiturates, clean reduction at the 2-position was able to be achieved <2002J(P1)2520>. 

Hydroborate Reduction. Lithium or sodium tetrahydroborate and diborane can be used for reduction of metal ions, especially light transition metal ions, to produce colloidal metals. For example, colloidal copper protected by polymer was prepared by reduction of copper(II) sulfate by a large excess of sodium tetrahydroborate in the presence of PVP or other polymers (12). A similar procedure for nickel(III) chloride produced nickel boride, not zero-valence nickel metal particles. 

Monodispersed, 2- to 6-nm-dia- Particles, formed from their metal salts by meter nickel boride, cobalt boride, NaBH4 reduction, were used as catalysts, nickel-cobalt boride, and iron Micellar core size controlled particle sizes... 

Paul Buisson Joseph Ind. Eng. Chem. 1952,44, 1006 Brown Chem. Commun. 1969,952. J. Org. Chem. 1970, 35. 1900. For a review of reductions with nickel boride and related catalysts, sec Canem Osby Chem. Rev. 1986, 86. 

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]. 

O-p-tolylsulfonyl-a-D-mannoside (39) in 37% yield. Treatment of (39) with sodium iodide in acetone gave the 6-iodo derivative (40), which underwent reduction with hydrogen in the presence of a nickel boride" catalyst" to give methyl 4-0-benzoyl-2,3-0 carbonyl-6-deoxy-o>-D-manno-side (41) in 95% yield. Reaction of (41) with hydrogen bromide in acetic acid effected replacement of the methoxyl group at C-l, affording crystalline... 

Reduction of derivatives of ally lie alcohols. Nickel boride can effect reduction of allylic alcohols to alkenes, but yields are generally improved by reduction of the acetates, benzoates, or trifluoroacetates.1 Reduction of allylic benzyl ethers to alkenes is effected in higher yield with Raney nickel. Methyl ethers are not reduced by either reagent. The trimethylsilyl ethers of allylic alcohols are reduced to alkenes by nickel boride in diglyme.2... 

RNOi- RNHi.1 Nickel boride catalyzes reductions of aliphatic nitro compounds by NaBH4. Ni2B alone is ineffective. Reduction with NaBH4-NiCl2 in aqueous 2-propanol is much slower and results in more by-products. 

Dichloro-2,2-difluoroethylene, 105 (Diethylamino)sulfur trifluoride, 110 Reduction reactions (see also Deoxygenation, Reductive. . . ) of acetals and ketals Dibromoalane, 237 Diisobutylaluminum hydride, 237 Triethylsilane-Tin(IV) chloride, 237 of acetates and other esters to alkanes Nickel boride, 197 Triphenylsilane, 334 of acyl halides to alcohols Sodium cyanoborohydride-Tin(II) chloride, 280... 

Magnesium-Methanol, 170 Miscellaneous reductions Cyanotrimethylsilane, 87 Nickel boride, 197 B -3-Pinany 1-9-borabicy clo[3. 3.1 ]no-nane, 249... 

When one component of a bimetallic alloy is leached out, a finely divided metal powder of high surface area results. One of the oldest of these so-called skeletal metal catalysts is Raney nickel10,11. Nickel boride is a more recently developed hydrogenation catalyst prepared by the reduction of nickel salts with sodium borohydride12-14. Bimetallic catalysts are often used to achieve selective saturation of a double bond in bifunctional unsaturated systems, e.g. in dienes. Amorphous metal alloys, a newly developed class of metal catalysts15,16, have also been applied in the hydrogenation of alkenes and dienes. 

Nickel, either as a Raney catalyst or in the form of nickel boride, is also effective in the reduction of the C=0 bond. An increase in the catalytic activity can be brought about by metal promoters (chromium and molybdenum). Copper chromite may also be used. 

Deselenation. C-Se bonds are cleaved reductively by nickel boride in methanol in generally high yield. This reduction can even be more facile than reduction of C=C bonds. 

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