Heptitol 2,6>-anhydro-3-deoxy

C19H23BrO10S 4,5,7-Tri-0-acetyl-2,6-anhydro-l-0-(p-bromophenylsul- fonyl)-3-deoxy-D-gluco-heptitol BACGLO 31 369... 

On deamination, l-amino-2,6-anhydro-l-deoxy-D-giycero-D-ga-Zacfo-heptitol (84) gave the corresponding anhydroheptitol (85) in 58% yield, plus the l-deoxy-2-heptulose 86, isolated in syrupy (17%) and crystalline (8%) forms.165 The rearrangement leading to the latter... 

Substitution was also the major reaction in the deamination of l-amino-2,6-anhydro-l-deoxy-D-allitol 67and l-amino-2,6-anhydro-l,7-dideoxy-L-g(i/cero-L-ga(acfo-heptitol.168 The rearrangement product, a l,6-dideoxy-2-heptulose, was also isolated from the latter amine, the ratio of substitution to rearrangement being 1.6 1. 

From the oxo reaction of 3,4,6-tri-O-acetyl-D-galactal (36) (after deacetylation of the mixture of products), there was obtained, in almost quantitative yield, 2,6-anhydro-3-deoxy-D-golacto-heptitol (37) and 2,6-anhydro-3-deoxy-D-foio-heptitol (38). - Structural investigations of these anhydrodeoxyalditols paralleled those on the alditols obtained from 3,4,6-tri-O-acetyl-D-glucal. The absolute structures of compounds (37) and (38) were unequivocally established by correlation, as shown, with 2,6-anhydro-3-deoxy-D-gZuco-heptitol (27). Prior structural work" on compound (37), with the aid of periodic acid degradations only, had led to an incorrect, tentative assignment of structure. 

Attempts to use 4,5,7-tri-0-acetyl-2,6-anhydro-l,3-dideoxy-l-iodo-D-giuco-heptitol for x-ray analysis were unsuccessful, because only twinned crystals could be prepared. Use of die deacetylated p-toluenesulfonate, namely, 2,6-anhydro-3-deoxy-l-0-p-tolylsulfonyl-D-gl co-heptitol, and of the parent alditol, 2,6-anhydro-3-deoxy-D-glaco-hepti-tol, was unsuccessful because no atom of sufficient electron density was present. 

Application of the oxo reaction to tetra-0-acetyl-l-deoxy-D-arob no-hex-l-enopyranose (49) (2-acetoxy-tri-O-acetyl-D-glucal ) produced mainly one product which, on deacetylation with sodium methoxide, readily afforded 2,6-anhydro-D-g/ycefo-D-gttZo-heptitol (50) in 70% yield. This compound had previously been described by Coxon and Fletcher, and their structural proof was used in the assignment of structure to compound (50). 

From the oxo reaction of tetra-O-acetyl-l-deoxy-D-Zt/xo-hex-l-eno-pyranose (51), with dicobalt octacarbonyl as the catalyst, followed by deacetylation of the mixture of products, the expected heptitol, namely, 2,6-anhydro-D-gZt/cero-L-manno-heptitol (52), was produced in much lower yield (about 20 %). 

The conversion of tetra-0-acetyl-l-deoxy-D-arabtno(and o-lyxo)-hex-l-enopyranose into 2,6-anhydro-D-gIj/cero-D-guIo(and L-manno)-heptitol, respectively, provides chemical proof that the oxo reaction proceeds by way of cis addition of hydroxymethyl and hydrogen to the carbon—carbon double bond. 

An isolated example of the use of x-ray diflraction analysis is provided by the work of Camerman and coworkers. Hydroformyl-ation of 3,4,6-tri-O-acetyl-D-glucal gave 4,5,7-tri-0-acetyl-2,6-anhydro-3-deoxy-D-gIuco- and -D-manno-heptitols, which were converted into the corresponding 1-p-bromobenzenesulfonates. One of these sulfonates was shown hy x-ray analysis to have the CJ(d) conformation in which all of the substituents are oriented equatorially hence, this sulfonate was the D-gluco isomer. 

Tetra-0-acetyl-2,6-anhydro-1-deoxy-D-g(/ycero-D-g(u/o-heptitol... 

Spontaneous reactions of the irreversible 8-D-galactosidase inhibitor 2,6-anhydro-l-deoxy-l-diazo-D-j-Zycero-L-ma/ino-heptitol have been investigated. ... 

Ester and sulphonium salt formation in the active-site labelling of jS-D-galacto-sidase from E. coli by 2,6-anhydro-l-deoxy-l-diazo-D- /ycera-L-manno-heptitol has been examined.2,6-Anhydro-l-deoxy-l-diazo-D- /yccro-L-wflnno-heptitol... 

P-D-Galactopyranosylmethyl- G-166 (1 - 4)-4-deoxy-D-galactose 4-C- (2,6-Anhydro-l-deoxy-D- ycero-L-manno-heptitol-l -yl) -4-deoxy-D-galactose... 

Aminotransferases, 31, 163, 164, see also specific enzymes Ampicillin, 536 A -Androstene-3,17-dione, 461 Angiotensin, 236 Anhyride analogs, 302-307 2,6-Anhydro-l-diazo-l-deoxy-D-glycero-i-OTonno-heptitol, 36... 

Tetra-0-acetyl-2,6-anhydro-l-deoxy-l-nitro-D-glycero-D-gulo-heptitol (14) [34] (4.0 g, 10.2 mmol)... 

Anhydro-l-deoxy-l-diazo-D- /ycerO L-wa wo-heptitol blocked the active site of the jS-D-galactosidase from Escherichia coli by the reaction shown in Scheme 14. An immunoassay for anti-adenosine antibodies is based on E. coli jS-D-galactosidase coupled to adenosine, the binding of the complex to the antibodies being measured with 2-nitrophenyl jS-D-galactopyranoside as a substrate. ... 

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