Sodium borohydride olefinic aldehydes

Sodium hydrogen telluride, (NaTeH), prepared in situ from the reaction of tellurium powder with an aqueous ethanol solution of sodium borohydride, is an effective reducing reagent for many functionalities, such as azide, sulfoxide, disulfide, activated C=C bonds, nitroxide, and so forth. Water is a convenient solvent for these transformations.28 A variety of functional groups including aldehydes, ketones, olefins, nitroxides, and azides are also reduced by sodium hypophosphite buffer solution.29... 

Phosphorylated allenes 195 (R1 = H or Me) are a source of secondary ( )-allylamines. The allenes are treated with an amine R2NH2 (R2 = t-Bu or 4-MeCgH4 and the products, which exist as equilibrium mixtures of enamines 196 and imines 197, are olefinated by successive reaction with methyllithium and an aldehyde R3CHO (R = i-Bu, 4-MeCgH4, PhCH2CH2 etc). Reduction with sodium borohydride finally yields the... 

Enamidines (2). Lithiation of 1 followed by treatment with aldehydes or ketones results in Peterson olefination to give a mixture of isomeric enamidines (2) in good yield. These enamidines can be used to convert the carbonyl compounds used in (heir preparation to homologated amines, aldehydes, and ketones. Conversion to a mclhylaminc involves reduction with sodium borohydride (pH 6) to an aminal, which is then hydrolyzed by dilute acid. The sequence can be carried out from 1 without isolation of any intermediates (equation I). 

The starting compound 251 was reduced to 252 with sodium borohydride. The latter was heated under reflux in 6% sulfuric acid in methanol to afford compound 253. Treatment of the latter with maleic anhydride at 170° for 3 hr afforded compound 254. Bisdecarboxylation of 254 with dicarbonyl bistriphenylphosphinenickel in anhydrous diglyme under nitrogen at reflux temperature for 6 hr afforded the olefin 255 in 69% yield (171). The latter was reduced with lithium aluminium hydride to the primary alcohol 256, which was oxidized to the aldehyde 257 with Ar,A -dicyclohexylcarbodiimide, dimethyl sulfoxide and pyridine in dry benzene. Treatment of the aldehyde 257 with an excess of the Grignard reagent prepared from l-bromo-3-benzyloxybutane afforded a mixture of diastereoisomers represented by the structure 258. 

Like alkene double bonds, carbonyl double bonds can be reduced by catalytic hydrogenation. Catalytic hydrogenation is slower with carbonyl groups than with olefinic double bonds, however. Before sodium borohydride was available, catalytic hydrogenation was often used to reduce aldehydes and ketones, but any olefinic double bonds were reduced as well. In the laboratory, we prefer sodium borohydride over catalytic reduction because it reduces ketones and aldehydes faster than olefins, and no gas-handling equipment is required. Catalytic hydrogenation is still widely used in industry, however, because H2 is much cheaper than NaBH4, and pressure equipment is more readily available there. 

The best reagents for reduction of olefinic aldehydes to olefinic alcohols are lithium aluminum hydride and sodium borohydride. Crotyl alcohol, CHjCH = CHCHjOH, and cinnamyl alcohol, CjH,CH =CHCHjOH, have been prepared in excellent yields. Cinnamyl alcohol is further reduced at higher temperatures to hydrocinnamyl alcohol. Citral, (CHj)jC =CHCHjCHjC(CH3)=CHCHO, may be selectively reduced to the ctOTesponding dienol by catalytic hydrogenation over platinum catalyst. A new method for the preparation of enediol esters of the type... 

Ozonolysis of the mixture of 35 and 36 followed by sodium borohydride reduction afforded 39 (86%) and 40 (6%) (Scheme 3)7 Detrityladon of 39 followed by Swem oxidation and Wittig olefination of the resulting aldehyde with Ph3P=CH(CH2)9CH3 furnished the Z-olefin 41 (49%) and the fi-olefin 42 (3%). The Z-olefin was hydrogenated and the oxazolidinone ring was saponified to produce (-)-desoxoprosopinine (4). 

A general synthesis for all diastereomeric L-hexoses, as an example for monosaccharides that often do not occur in the chiral pool, has been worked out. The epoxidation of allylic alcohols with tertiary butyl hydroperoxide in presence of titanyl tartaric ester catalysts converts the carbon-carbon double bond stereose-lectively to a diol and is thus ideally suited for the preparation of carbohydrates. The procedure is particularly useful as a repetitive two-carbon homologiza-tion in total syntheses of higher monosaccharides and other poly hydroxy compounds. It starts with a Wittig reaction of a benzylated a-hydroxy aldehyde with (triphenylphosphoran-ylidene)acetaldehyde to produce the olefinic double bond needed for epoxidation. Reduction with sodium-borohydride... 

The reduction of 569e with lithium aluminum hydride followed by monoprotection with er -butyldimethylsilyl chloride and Dess-Martin oxidation of the free hydroxyl group to an aldehyde affords 610. An aldol reaction of 610 with ( S)-(y-alkoxyallyl)stannane (611) in the presence of boron trifluoride etherate provides exculsively, in 80% yield, the alcohol 612. Ozonolysis of the olefin followed by sodium borohydride reduction affords diol 613, which is converted to acetonide 614 (Scheme 135). Interestingly, alcohol 612, the double bond of which is susceptible to stereocontrolled introduction of hydroxyl groups, could lead to o)-deoxy sugars [197]. 

Sodium hydrogentelluride looks to be a very useful reagent for the reduction of the olefinic bond in a,/S-unsaturated carbonyl compounds (esters, aldehydes, ketones, coumarins). Yields by g.l.c. are virtually quantitative with this reagent, which is prepared in situ from sodium borohydride and tellurium powder. 

The next stage of the synthesis called for conversion of the terminal olefin to an aldehyde. This was accomplished using a Johnson-Lemieux oxidation. The resulting ketoaldehyde was then converted to fr-ketal 15. Basic hydrolysis of the formamide provided 16 and hydrolysis of the acetals afforded a mixture of diastereometic enaminoketones 17. An acid-promoted intramolecular Mannich reaction gave 2. Presumably epimerization of the ketone allowed both diastereomers of 17 to follow the path to 2. Reduction of ketone 2 with sodium borohydride provided an alcohol, which underwent formal dehydration upon treatment with thionyl chloride and pyridine, to give porantherine (1) as a racemic mixture. 

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