O-sulfonyl

Closely related is the reaction of enamines with O-sulfonyl lactams (411-413), which has extended the versatility of Hiinig s carboxylic acid extension sequence to compounds with a terminal amine function. 

Bei 2,2,2-Trichlor-athanolen bzw. deren O-Sulfonyl- bzw. O-Acyl-Derivaten wird in saurem Medium in einer Sekundar-Reaktion teilweise unter Abspaltung von Sulfonsaure bzw. Carbonsaure das 1,1-Dichlor-athen-Derivat erhalten ... 

N-Diphenylmethylen- 374 N-Diphenylmethylen-O-aminocarbonyl- 612 N-[l,3-Diphenyl-propyl-(2) - 374 N-[l,3-Diphenyl-propyliden-(2)]- 374, 377, 380 N-(4-Halogen-phenyI)- 683 N-Heptyl- 375 N-Heptyl-N-acetyl- 376 N-Heptyliden- 375 N-Hcptyliden-O-acetyl- 376 0-(2-Hydroxy-athyl)-N-athoxycarbonyl- 133 N-(4-Hydroxy-phenyl)- 683 0-(2-Hydroxy-l-phenyl-athyI)-N-athoxycarbonyI-aus 0-(ci-AthoxycarbonyI-benzyl)-N-athoxycar-bonyl-hydroxylamin und Lithiumalanat 133 N-Isopropyl- 682 N-Isopropylidcn- 613 N-Methyl- 133, 682 O-Methyl-N-bcnzyliden- 377 O-Methyl-N-benzyliden- 375 0-Methyl-N-(4-chlor-benzyl)- 375 0-Methyl-N-(4-chlor-benzyliden)- 375 N-Methy -N,0-diacetyI- 682 N-(4-Methyl-phenyl)- 683 0-McthyI-N-( 1 -phenyl-athyliden)- 375 N-(4-Methylthio-phenyl)- 684 N-(4-Nitro-benzyl)- 374 N-[4-Nitro-benzyliden - 374, 377 N-(2-Nitro-phenyl)- 562 N-(4-Nitro-phenyl)- 682 N-Nitroso-N-cyclohexyl- 697 N-Octyl- 374 N-Octyl-(2)-N-acetyl- 376 N-Octyliden- 374 N-0ctyliden-(2)-0-acctyl- 376 N-(Pentafluor-phenyl)-0,N-diacetyl- 697 N-Phenyl- 474, 481, 682, 783 N-Phenylacetyl-O-benzoyl- 265 N-(l-Phenyl-athyl)- 374 N-(l-Phenyl-athyl)-N-acetyl- 376 N-(l-Phenyl-athyliden)-374, 613 N-( l-Phenyl-athyliden)-0-acetyl- 376 N-[ 1 -Phenyl-buten-( 1 )-yl-(3)-iden]- 582 N-f4-Phenyl-butyl-(2)-iden]- 581 N-Phcnyl-N,0-diacetyl- 682 N-(4-Phenylthio-phenyl)- 684 N-Propyl-N-cyclohexyl- 376 N-Propyl-N-isopropyl- 376 O-Sulfonyl- 481 N-(4-Sulfonyl-phenyI)- 683 N-(2-Vinyl-phenyl)- 698... 

N-Hydroxy arylamines are also converted to N-acetoxy arylamines (V), but apparently by an acetyl coenzyme A-dependent enzymatic O-esterification (7, 8). Similarly, N-sulfonyloxy arylamines (VI) are thought to arise by a PAPS-dependent enzymatic O-sulfonylation of N-hydroxy arylamines (9,10) while 0-seryl or 0-prolyl esters (VII) are formed by their corresponding aminoacyl tRNA synthetases in a ATP-dependent reaction (11,12). 

The simplified preparations128 of 5-O-sulfonylated derivatives of 1,2-O-isopropylidene-a-D-gIucofuranose (77 and 78) (see Section VI,4) was the key to substantial improvements in the synthesis of L-idose. 

The value of 0.05 M from equation (7) is consistent with values of A as < 1 and ( /fes) < 1 for reactions in water. For example, = 0.3 gives (Jdjki ) = 0.17 for the relative rate constants for addition of solvent to the carbocation-anion pair and free carbocation. By comparison, the three-fold smaller rate constant for addition of water to an intramolecular trityl carbocation-sulfonate ion pair compared with addition to the analogous substituted trityl carbocation o-sulfonyl methyl ester has been used to estimate a value of (kjk ) = 0.33. " ... 

The three l,4 3,6-dianhydrohexitols show the shielding effect of the cts-fused oxolane ring on their di-O-sulfonyl derivatives. As C-2 and C-5 of 1,4 3,6-dianhydro-D-mannitol 2,5-di-p-toluene-sulfonate and 2,5-dimethanesulfonate are open to attack from the exo direction, they react readily with such nucleophilic reagents as benzoate in /V,iV-dimethylfoimainide,94 acetate in acetone,93 thioacetate,95 phthalimide in A/,JV-dimethylformamide,93 and iodide in acetic anhy-dride.59<6) Inversion occurs at these positions and the L-iditol configuration results, as pointed out in the several examples in Table V. However, hydroxide ion may merely saponify,92 with retention of configuration.93... 

Methyl 6-amino-6-deoxy-a-D-gIucopyranoside derivatives 2 c were synthesized in our laboratory by a somewhat different procedure [31]. 6-O-Sulfonyl or 6-bromo-6-deoxy derivatives of methyl a-D-glucopyranoside were substituted at C-6 by sodium azide. The 6-azido-6-deoxy intermediate was then treated by acyl chlorides in the presence of triphenylphosphine (Staudinger reaction) to afford amido derivatives which were finally de-O-acetylated to give 2 c. The same reaction pathway allowed the preparation of 6-alkylamido-6-deoxy-D-glucopy-ranose derivatives, starting from D-glucose [31]. 

These heterocyclic compounds undergo many reactions which are similar to those of the acetone enolate. Thus, Claisen condensation and o-sulfonylation are exemplified by Scheme 57. 

Jones and Nicholson234 have observed that treatment of 2-O-sulfonyl sugars with base leads to epimerization at C-2. In this way, 2-O-p-tolyl-sulfonyl-L-fucose (42) was converted into 6-deoxy-L-talose (44) in high yield. A possible intermediate might be the 1,2-anhydro sugar (43). 

O-Sulfonylation (MeS02Cl or PhCH2S02Cl/C5H5N) of 5-hydroxy-benzo[6]thiophene gives 5-methane- or 5-benzylsulfonyloxybenzo[6]-thiophene, respectively,337 and with epichlorohydrin it affords 5-(3-chloro-2-hydroxypropoxy)benzo[6]thiophene.613 Potential pesticides, analogous to those described in Section VI, 1,3, have been prepared from 5-hydroxybenzo[6]thiophene.610,612... 

Some other mono-O-sulfonylated-aldose derivatives to which the iodination reaction has since been successfully applied (either prepara-tively or diagnostically, or both) are listed in Table III. The yields given therein are those recorded by the authors, and have not been recalculated. Where the yield approaches the theoretical, there is seldom any indication that the same yield might not have resulted at a lower temperature or after a shorter reaction-time, or both. Low yields might, in some instances, be attributable to poor experimental technique. However, despite its deficiencies, Table III contains sufficient information to warrant a few conclusions, some of which are to be found scattered through the literature. 

Replacement, by Iodine, of Primary Sulfonyloxy Group of Mono-O-sulfonyl-aldose... 

Soon after the appearance of Oldham and Rutherford s classic paper,20 Levene and his school began a systematic study of the behavior of cyclic-sugar derivatives bearing only secondary O-sulfonyl groups. In 1933, they found that 5,6-0-benzylidene-l,2-0-isopropylidene-3-0-tosyl-D-glucose is completely unaffected361 under Oldham and Rutherford s conditions, but that the sulfonyloxy groups of 5-O-acetyl- and 5-0-benzoyl-l,2-0-... 

Action of Sodium Iodide on Cyclic-Sugar Derivatives Containing Secondary O-Sulfonyl... 

Lithium chloride, preferably dissolved in absolute ethanol, has also been used306 419 420 for preparing alkyl chlorides. Dissolved in absolute ethanol-acetone (1 1, by vol.), it has recently414 found application with alditol sulfonates. Its action on l,4 3,6-dianhydro-2,5-di-0-mesyl-L-iditol, l,4 3,6-dianhydro-2,5-di-0-mesyl-D-mannitol, and l,4 3,6-dian-hydro-2,5-di-0-mesyl- (and -2,5-di-O-tosyl-) sorbitol resembles the action of sodium iodide on these compounds, i.e., the first displays no appreciable reaction, the second gives the 2,5-dichloro-2,5-dideoxy derivative, and the last two afford the respective monochloromonodeoxy-mono-O-sulfonyl derivatives. Treatment of l,4 3,6-dianhydro-2,5-di-0-mesyl-sorbitol during 48 hours at 180-90° gives some of a dianhydro-mono-chloromonodeoxy-sorbitoleen. 

This is very similar to the above method of conversion of pyridinium Ar-imides to 1,2-diazepines. Here the tetrahydrocarbolines <1996CHEC-II(9)113> or the tetrahydroisoquinolines <1984CHEC(7)593> are N-substituted and N-aminated with O-sulfonyl hydroxylamine derivatives followed by treatment with base to give the corresponding 1,2-diazepines. 

Enol sulfonates. Sulfonylation of enolate anions with 1 is markedly affected by the gegenion. Lithium enolates undergo mainly C-sulfonylation. Cesium or quaternary ammonium enolates undergo regioselective O-sulfonylation. The same behavior is observed with nonailuorobutanesulfonyl fluoride.1... 

Polymeric structure of o-sulfonyl iodosylbenzene 135 with tetracoordinated iodine of pseudo square planar geometry was obtained by the single crystal X-ray analysis (Fig. 5) [217]. The bright yellow A3-iodane 135 is soluble in chloroform because of the weaker intermolecular hypervalent interaction (I-OT, 2.665 A) compared to that of iodosylbenzene 18 [218]. 

Fig. 8.9. O-Sulfonylation of the asymmetric /V,A/-dialkyl urea A with tosyl chloride/ triethylamine and subsequent, deprotonation to the unsymmetrical N,N dialkylcarbodiimide D.

Fig. 13.23. O-Sulfonylations of regioisomeric ketone eno-lates to give an enol trifLate (regarding the regiocontrol of the enolate formations cf. the discussion of Figure 13.11) ...

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