Synthesis of 4-Acetamido-1,2,3,5-tetra-O-acetyl-4-deoxy-D-ribofuranose. A Pyrrolidine Sugar<sup>1-3</sup>

Reist, Elmer J.; Gueffroy, Donald E.; Goodman, Leon

doi:10.1021/ja01081a066

Cited by 17 publications

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“…(7) observed a similar selective replacement reaction of methyl 2-0-acetyl-3,4-di-0-toluei1e-p-sulfonyl-~-~-arabinopranoside with sodiunl azide in N,N-dimethylformamide, and thereby achieved the synthesis of 4-acetamido-4-deoxy-D-ribose. 4-Acetamido-4-deoxy-1,-xylose has been synthesized froill methyl tri-0-methanesulfonyla-D-xyloppranoside (I) (6).…”

Section: -mentioning

confidence: 90%

Selective Nucleophilic Substitution and Preferential Epoxide Formation

Dick¹,

Jones²

1966

Can. J. Chem.

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The tri-0-methanesulfonyl derivatives of methyl a-D-sylopyranoside, methyl 8-L-arabinopyranoside, and methyl a-L-arabinopyranoside undergo selective substitutio~~ a t C-4, when heated with sodium azide in N,N-dimethylforma~nide, to yield 4-azido derivatives with inversion of configuration a t C-4. The resultant 4-azido-2,s-di-0-methanesulfonyl derivatives were converted, by reaction with sodium methoxide, into 2,s-anhydro compounds whose configurations were assigned by nuclear magnetic resonance analysis. The mechanism of epoxide formation is discussed. ISTRODUCTIONThe many attempts t o effect nucleophilic substitution of isolated sulfonate ester groups attached t o furailoside and pyranoside rings have met with only limited success ( I ) , although the replacement of 4-sulfonates of certain hexopyranosides has been achieved (2), as has also the replacement of the 3-toluene-P-sulfonyl-P-D-glucopyranose (3). T h e course of the reactions of tosyl derivatives of cyclitols with sodium benzoate in N,Ndilnethylforn~amide has also been described (4). The present study is concerned with the con~petitive nucleophilic substitution of methyl 2,3,4-tri-0-methanesulfonyl-pentopyranosides with azide ion in N,N-dimethylformamide solution. This work was prompted by a related investigation of the reaction of methyl hexopyranoside tetrachlorosulfates with chIoride ion (5), to ~vhich the results reported here are strictly analogous.The 2,3,4-tri-0-inethanesulfonyl derivatives of methyl a-D-xylopyranoside (I) (G), methyl P-D-xylopyranoside (11), methyl P-L-arabinopyranoside (III), and methyl a-L-arabinopyranoside (IV) were each caused to react with 1 illole of sodium azide in N,N-diinethylforinamide a t 130' to yield 4-azido-4-deoxy derivatives with inversion of configuration a t C-4. Thus the 4-azido-4-deoxy-2,3-di-O-inethanesulfonyl derivatives of methyl P-L-arabinopyranoside (V) (G), methyl a-L-arabinopyranoside (VI), inethyl a-D-xylopyranoside (VII), and methyl P-D-xylopyranoside (VIII) were obtained from I , 11, 111, and IV, respectively. Of the four azido-di-0-methanesulfonyl derivatives described, only inethyl 4-azido-4-deoxy-2,3-di-O-i11ethanesulfonyl-~-~-xylopyranoside (VIII) could be substituted further in the presence of an excess of sodium azide; these results will be described in a later publication.T h a t V, VI, and VII were resistant to further substitution may be rationalized according to the arguinents put forward by Jennings and Jones (5). T h e ester group on C-2 would be expected to be unreactive as coinpared nrith those on C-3 and C-4 because of their different electronic environments, that on C-2 being in the proximity of t~v o P-oxygen atoins (ring oxygen and anomeric groups). I-Iindrance to attaclc a t the rear side of the sulfonyloxy groups a t C-3 of V and VII by the axial methyl glycosidic group would prevent further substitution in these compounds. T o explain the unreactivity of the ester group a t C-3 of VI it is necessary to invoke deactivation of the equatorial ester group by the vicinal ax...

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Section: -mentioning

confidence: 90%

Selective Nucleophilic Substitution and Preferential Epoxide Formation

Dick¹,

Jones²

1966

Can. J. Chem.

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“…In fact, tosylation of methyl 2-O-benzoyl-b-L-arabinopyranoside with an excess of tosyl chloride gave 46% of the 3,4-di-O-tosyl derivative. 10 In contrast, the methylsulfonylation (mesylation) shoud be more readily accomplished. 11 As expected, the mesylation of 4 took place in a shorter time than the tosylation and the yield of the dimesylate 6 was higher (90%).…”

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Enantiospecific Synthesis of Both Enantiomers of 2-Benzyloxydihydropyran-3-ones from Arabinose

Uhrig¹,

Varela²

2005

Synthesis

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Approaches to the enantioselective synthesis of the useful building blocks (2R)-and (2S)-2-benzyloxy-2(H)-pyran-3(6H)-one (12 and 17, respectively) are described. The most direct and highly yielding route for the synthesis of 12 was based on the 'onepot' preparation of benzyl 2-O-acetyl-arabinopyranoside 3,4-thionocarbonates (7 and 14) from benzyl b-L-or b-D-arabinopyranosides (1 and 13). Trimethylphosphite-promoted olefination, followed by O-deacetylation and oxidation gave the optically pure enantiomeric enones 12 and 17 in about 50% overall yield.

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Kohlenhydrate mit Stickstoff oder Schwefel im „Halbacetal”︁‐Ring

Paulsen

1966

Angewandte Chemie

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Synthesis of 4-Acetamido-1,2,3,5-tetra-O-acetyl-4-deoxy-D-ribofuranose. A Pyrrolidine Sugar^1-3

Cited by 17 publications

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Selective Nucleophilic Substitution and Preferential Epoxide Formation

Selective Nucleophilic Substitution and Preferential Epoxide Formation

Enantiospecific Synthesis of Both Enantiomers of 2-Benzyloxydihydropyran-3-ones from Arabinose

Kohlenhydrate mit Stickstoff oder Schwefel im „Halbacetal”︁‐Ring

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Synthesis of 4-Acetamido-1,2,3,5-tetra-O-acetyl-4-deoxy-D-ribofuranose. A Pyrrolidine Sugar1-3

Cited by 17 publications

References 0 publications

Selective Nucleophilic Substitution and Preferential Epoxide Formation

Selective Nucleophilic Substitution and Preferential Epoxide Formation

Enantiospecific Synthesis of Both Enantiomers of 2-Benzyloxydihydropyran-3-ones from Arabinose

Kohlenhydrate mit Stickstoff oder Schwefel im „Halbacetal”︁‐Ring

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Synthesis of 4-Acetamido-1,2,3,5-tetra-O-acetyl-4-deoxy-D-ribofuranose. A Pyrrolidine Sugar^1-3