3-Amino-l,2-diols

Amino-l, 2-diols.4 In the presence of this vanadium(II) reagent, N-protected a-amino aldehydes undergo pinacol coupling with aliphatic aldehydes to provide syn, syn-3-amino-l,2-diols as the major product (5-50 1). 

The cyclic (iodomethyl)carbamates 15 can be easily converted into 3-amino-l,2-diol derivatives 17 via iodine displacement with Amberlyst A-26 in the acetate form. In addition, cleavage of the carbon- iodine bond (lithium aluminum hydride or tributyl tin hydride) leads to the trans-2-oxazolidinones 18, which are useful intermediates for the synthesis of 1,2-iyn-amino alcohol systems 199 12. 

Dihydromuscimol (49) is a conformationally restricted analogue of the physiologically important neurotransmitter y-aminobutyric acid (GABA) and has been prepared using the cycloaddition of dibromoformaldoxime to A-Boc-allylamine followed by N-deprotection with sodium hydroxide (Scheme 6.52) (278). The individual enantiomers of dihydromuscimol were obtained by reaction of the bromonitrile oxide with (5)-( + )-l,2-0-isopropylidene-3-butene-l,2-diol, followed by separation of the diastereoisomeric mixture (erythro/threo 76 24), hydrolysis of respective isomers, and transformation of the glycol moiety into an amino group (279). 

In a totally selective ring opening of amino epoxides with ketones, enantiopure (2R,3S)- and (2S,3S)-3-aminoalkane-l,2-diols have been prepared in high yield, total diastereoselectivity, and without epimerization, using BF3.Et20 catalysis.335... 

Studies with the male antifertility agents 3-chloropropane-l,2-diol and 3-amino-l-chloropropane-2-ol have indicated that the antifertility activity in rat is due to the 5-enantiomers, whereas the i -enantiomers are associated with nephrotoxicity [160,161]. Metabolic studies indicated that a common metabolite was the causative agent, which was postulated to be (i )-3-chlorolactate. Administration of the enantiomers of 3-chlorolactate to rats resulted in elevated urinary excretion of oxalate, presumably formed via oxidation of the intermediate 3-chloropyruvate, a known inhibitor of renal... 

Ammonium-directed metal-free oxidation of cyclic allylic and homoallylic amines has been reviewed. Such reactions yield all four diastereoisomers of the corresponding 3-amino-1,2-diols, and have featured in recent syntheses of ( )-l-deoxynojirimycin and ( )-l-deoxyaltronojirimycin. ... 

M. Egi, K. Azechi, S. Akai, CationicGold(l)-mediatedintramolecular cyclization of 3-alkyne-l,2-diols and l-amino-3-aIkyn-2-ols a practical route to furans and pyrroles, Org. Lett. 11 (2009) 5002-5005. 

In contrast to many studies on cycloaromatization via transition metal-vinylidene complexes as key reactive intermediates, only one example of such a reaction via transition metal-allenylidene complexes has been reported to date. In 2008, Yada et al. reported the formation of substituted fiirans 78 from 3-butyne-l,2-diols 77 in the presence of a catalytic amount of thiolate-bridged diruthenium complex (Scheme 21.33) [45]. This methodology was also applied to the formation of a substituted pyrrole 80 from l-amino-2-butyn-2-ol 79. It is noteworthy that thiolate-bridged diruthenium complexes worked as effective catalysts toward cyclization involving both ruthenium-allenylidene and ruthenium-vinylidene complexes as key reactive intermediates. 

Fig. 2. Ultrafiltered plutonium nitrate (50 pi) was added to an aqueous solution of 2,3-dihydroxy-benzoyl-N-glycine (0.05M), pH 3.5. The resulting solution (1.5 ml) was eluted from Sephadex G-50 (0.9 x 60 cm) with 0.1M 2-amino-2-hydroxymethylpropane-l,2-diol/lM NaCl, pH 8.0...

High anti-diastereoselectivity is observed for several aromatic imines for ortho-substituted aromatic imines the two newly formed stereocenters are created with almost absolute stereocontrol. Aliphatic imines can also be used as substrates and the reaction is readily performed on the gram scale with as little as 0.25 mol% catalyst loading. Furthermore, the Mannich adducts are readily transformed to protected a-hydroxy-/8-amino acids in high yield. The absolute stereochemistry of the Mannich adducts revealed that Et2Zn-linked complex 3 affords Mannich and aldol adducts with the same absolute configuration (2 R). However, the diastereoselectiv-ity of the amino alcohol derivatives is anti, which is opposite to the syn-l,2-diol aldol products. Hence, the electrophiles approach the re face of the zinc enolate in the Mannich reactions and the si face in the aldol reactions. The anti selectivity is... 

Mayeno et al.8 reported that PAA could become metabolized to 3-phenyl-amino-l,2-propane-diol (PAP), a compound that was found to be contaminating the rapeseed oil consumed by individuals who developed the toxic oil syndrome in Spain in 1981.74... 

Dihydroxy-4-(l-hydroxyethyl) -4-cyclopenten-l-yljadenine. 5-(6-Amino-9ii-purin-9-yl) -3- (1-hydroxy ethyl) -3-cyclopen-tene-l,2-diol, 9CI. TJ13025... 

Johnson and coworkers [47] have synthesized (l->6)-, (l->4)-, and (1->1)-linked aza-C-disaccharides D-azaMan- -Jl->6)-D-Man(8), D-azaMan-(3-(1->6)-d-G1c(9), D-azaMan-(3-(l->4)-D-Talo(10) and D-azaMan-P-(l-> 1)-D-P-Glc(ll). The polyhydroxylated piperidine ring is constructed employing vinylbromide, (3R,4R,5S,6S)-3-[(N-benzyloxycarbonyl)amino]-l-bromo-4-[(tert-butyldimethylsilyl)oxy]-5,6-(0-isopropylidenedioxy)cyclohex-l-ene(12), as a common intermediate for these sugars. Vinylbromide (12) required for Suzuki coupling is synthesized de novo from 3-bromocyclohex-3,5-dien-l,2-diol as outlined in Scheme 31.12 [47]. 

Decomposition of ketosamines starts, like most other reactions of monosaccharides, by 1,2-enoKsation that yields an amino analogue of l-ene-l,2-diol, which is l-ene-l-amino-2-ol (Figure 4.86). The reaction proceeds by elimination of the C-3 hydroxyl group and hydrolysis of the bound amino compound provides 3-deoxy-o-erythro-hexos-2-ulose and, further, 3,4-dideoxy-D-g/ycero-hex-3-enos-2-ulose, 5-hydroxymethylfuran-2-carbaldehyde in addition to other products that are formed by degradation of glucose by... 

Nenajdenko et al. obtained regioisomeric S-CFj or 7-CF3 triazolopyrimidines 154, 155 by the reaction of l,l,l-trifluoro-4-sulfonyl-but-3-ene-2,2-diol with 3-amino-1,2,4-triazole [135]. 

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