Glycine -Butyl Ester

Hydrazoic add, reaction with cyclobu-tanecarboxylic acid, 47, 28 Hydrogenation of /-butylazidoacetate to glycine 1-butyl ester, 46,47 Hydrogen bromide, 46, 43 reaction with y-butyrolactone, 46, 43 Hydrogen fluoride, anhydrous, precautions in use of, 46, 3 in preparation of nitronium tetra-fluoroborate, 47, 57 reaction with benzoyl chloride, 46,4 with boron trifluoride in conversion of -cyrnene to m-cymene, 47, 40 in bromofluorination of 1-heptene, 46, 11... 

Palladium-on-charcoal in reduction of 1-butyl azidoacetate to glycine 1-butyl ester, 46, 47... 

To 50 ml. of a well-cooled 6N sodium hydroxide solution is added, with stirring, 32 g. (0.15 mole) of the phosphite salt. The stirring is continued until all the solid has dissolved. The solution is transferred to a 125-ml. separatory funnel, extracted with three 20-ml. portions of ether, and the combined extracts dried over anhydrous sodium sulfate. The drying agent is removed by filtration, the solvent removed under reduced pressure, and the glycine 1-butyl ester distilled, b.p. 65-67° (20 mm.), ft20d 1.4237, yield 14 g. (72%, based on phosphite salt). The overall yield from 1-butyl chloroacetate is 50-55%. 

Glutaronitrile, 3-hydroxy-, 46, 48 Glycerol chlorohydrin, 46, 24 Glycine (-butyl ester, 45, 47 conversion to acetamidoacetone, 45,1 Glyoxal, phenyl-, 48,109 Glyoxals from esters and the potassium salt of dimethyl sulfoxide, 48, 112... 

Palladium-on-charcoal in reduction of (-butyl azidoacetate to glycine (-butyl ester, 46, 47 Pelargonyl fluoride, 46, 6 3,3-Pentamethylenediazirine, 46, 83 oxidation to 3,3-dimethyIazarine by silver oxide, 46, 83 Peroxyvanadic acid, 46, 27 Phenanthrene, 9-phenyi, 46, 91 Phenol, 46, 90... 

Glycine <-butyl ester is a valuable intermediate for the preparation of peptides of glycine, since the labile /-butyl group can readily be removed by add under conditions which do not affect the blocked amino grouping. The present method using /-butyl chloroacetate is superior to that using the bromo derivative, since chloride is cheaper to prepare, less lachrymatory and more easily separated, by fractional distillation, from the /-butyl azidoacetate. The method is also less cumbersome than the procedure using isobutene. 

The Maruoka group recently reported an alternative concept based on a one-pot double alkylation of the aldimine of glycine butyl ester, 44a, in the presence of the chiral ammonium salt 29 as chiral phase-transfer catalyst (the principal concept of this reaction is illustrated in Scheme 3.18, route 2) [58], Under optimized reaction conditions products of type 43 were obtained in yields of up to 80% and with high enantioselectivity (up to 98% ee). A selected example is shown in Scheme 3.20. 

This method is a modification of that developed by Vollmar and Dunn.3 Glycine /-butyl ester also has been prepared by the acid-catalyzed addition of TV-benzyloxycarbonylglycine to isobutene, followed by catalytic hydrogenolysis of the resulting N-benzyloxycarbonylglycine /-butyl ester.4 The esters of other amino acids have beeii prepared directly by the isobutene method.5... 

Condensation of the hydroxy acid (241) with glycine /-butyl ester hydrochloride (242) smoothly proceeds in the presence of DEPC and NEt3 to give the amide (243).89 Amide 243 is used as an intermediate for the synthesis of topostin B567 (244) and topostin D654 (245) both have proved to be novel inhibitors of mammalian DNA topoisomerase.89... 

Aminolysis of epoxides. The reaction of epoxides with glycine /-butyl ester is catalyzed by silica gel and promoted by high pressure. 

Palladium catalyst foe partial ee DUCTION OF ACETYLENES, 46, 89 Palladium on charcoal, catalyst for reductive methylation of ethyl p-mtrophenylacetate, 47, 69 in reduction of l butyl azidoacetate to glycine J-butyl ester 4B, 47 Palladium oxide as catalyst for reduction of sodium 2 nitrobenzene sulfinate, 47, S... 

Exposure of compound 16, a substance that can be obtained in a straightforward manner from glycine, to sodium tert-butoxide furnishes an enolate that undergoes conversion to 8 upon treatment with terf-butyl formate. It was anticipated that the phthalimido and tert-butyl ester protecting groups in 8 could be removed easily and selectively under anhydrous conditions at a later stage in the synthesis. 

Glycine ethyl ester hydrochloride, 14, 46 16, 86 17, 92 Grignard reaction in -butyl ether, 11, 84 with acetaldehyde, 12, 48 with butyl p-toluenesulfonate, 10, 4 with carbon dioxide, 11, 80 with dimethyl sulfate, 11, 66 with ethyl carbonate, 11, 98... 

A. 2-Bromo-N-Boc-glycine tert-butyl ester. In a 1-L, round-bottomed flask are placed 20.0 g (0.0865 mol) of N-Boc-glycine tert-butyl ester (Note 1) and 16.2 g (0.0912 mol) of N-bromosuccinimide (Note 2). Carbon tetrachloride (350 mL, Note 3)... 

Boc-Glyctne tert-butyl ester can be prepared by treatment of glycine teit-butyl ester hydrochloride (Aldrich Chemical Company, Inc.) with di-tert-butyl dicarbonate (Fluka Chemical Corporation) and triethylamine in THF.2... 

N-Boc-2-Bromoglycine tert-butyl ester (1), introduced Steglich and coworkers, is a versatile synthon for electrophilic glycine,5 an tnpcDortant tool in the synthesis of non-proteinogenic amino acids. 

Bromo-N-Boc-glycine-tert-butyl ester Acetic acid, bromo[[(1,1-dimethylethoxy)-carbonyl]amino]-, 1,1-dimethylethyl ester, (+)-, (12) (111652-22-3) N-Boc-Glydne-tert-butyl ester Glycine, N-[(1,1-dimethylethoxy)carbonyl)-, 1,1-dimethylethyl ester (12) (111652-20-1)... 

Glycine tert-butyl ester hydrochloride Glydne, tert-butyl ester, hydrochloride (8) Glycine, 1,1-dimethylethyl ester, hydrochloride (9) (27532-96-3)... 

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