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Biocatalytic route to C-3?-azido/-hydroxy-C-4?-spiro-oxetanoribonucleosides

Biocatalytic route to C-3?-azido/-hydroxy-C-4?-spiro-oxetanoribonucleosides
Biocatalytic route to C-3?-azido/-hydroxy-C-4?-spiro-oxetanoribonucleosides
The lipase, Novozyme®-435, exclusively deacetylates the 5-O-acetyl over 4-C-acetyloxymethyl group of almost identical reactivity in 5-O-acetyl-4-C-acetyloxymethyl-3-azido-3-deoxy-1,2-O-isopropylidene-?-D-ribofuranose that led to the development of first and efficient synthesis of 3?-azido-/3?-amino-C-4?-spiro-oxetanoribonucleosides T, U, C and A in 20–24% overall yields. The X-ray study on the compound obtained by tosylation of lipase-mediated monodeacetylated product unambiguously confirmed the point of diastereoselective monodeacetylation on diacetoxy-azido-ribofuranose derivative. The capability of Novozyme®-435 for selective deacylation of 5-O-acetyl group in 5-O-acetyl-4-C-acetyloxymethyl-3-O-benzyl-1,2-O-isopropylidene-?-D-ribofuranose recently discovered by us has been successfully used for the synthesis of C-4?-spiro-oxetanoribonucleosides A and C in good yields. These results clearly indicate that the broader substrate specificity and highly selective capability of Novozyme®-435 for carrying out acetylation/deacetylation reactions can be utilized for the development of environment friendly selective methodologies in organic synthesis.
biocatalysis, lipase, Novozyme®-435, diastereoselectivity, azido-spironucleosides
0008-6215
19-26
Kumar, Manish
04737164-0164-4f32-afe5-7346646d0ffd
Sharma, Vivek K.
b1eae149-9db0-49de-8159-c58d8cfda375
Kumar, Rajesh
5c0b5d03-f2e4-4e6e-a242-0482e5fb4264
Prasad, Ashok K.
baf9a13d-b8ab-4d88-a038-b028ad9bbf00
Kumar, Manish
04737164-0164-4f32-afe5-7346646d0ffd
Sharma, Vivek K.
b1eae149-9db0-49de-8159-c58d8cfda375
Kumar, Rajesh
5c0b5d03-f2e4-4e6e-a242-0482e5fb4264
Prasad, Ashok K.
baf9a13d-b8ab-4d88-a038-b028ad9bbf00

Kumar, Manish, Sharma, Vivek K., Kumar, Rajesh and Prasad, Ashok K. (2015) Biocatalytic route to C-3?-azido/-hydroxy-C-4?-spiro-oxetanoribonucleosides. Carbohydrate Research, 417, 19-26. (doi:10.1016/j.carres.2015.08.015). (PMID:26386197)

Record type: Article

Abstract

The lipase, Novozyme®-435, exclusively deacetylates the 5-O-acetyl over 4-C-acetyloxymethyl group of almost identical reactivity in 5-O-acetyl-4-C-acetyloxymethyl-3-azido-3-deoxy-1,2-O-isopropylidene-?-D-ribofuranose that led to the development of first and efficient synthesis of 3?-azido-/3?-amino-C-4?-spiro-oxetanoribonucleosides T, U, C and A in 20–24% overall yields. The X-ray study on the compound obtained by tosylation of lipase-mediated monodeacetylated product unambiguously confirmed the point of diastereoselective monodeacetylation on diacetoxy-azido-ribofuranose derivative. The capability of Novozyme®-435 for selective deacylation of 5-O-acetyl group in 5-O-acetyl-4-C-acetyloxymethyl-3-O-benzyl-1,2-O-isopropylidene-?-D-ribofuranose recently discovered by us has been successfully used for the synthesis of C-4?-spiro-oxetanoribonucleosides A and C in good yields. These results clearly indicate that the broader substrate specificity and highly selective capability of Novozyme®-435 for carrying out acetylation/deacetylation reactions can be utilized for the development of environment friendly selective methodologies in organic synthesis.

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Accepted/In Press date: 26 August 2015
e-pub ahead of print date: 31 August 2015
Published date: 19 November 2015
Keywords: biocatalysis, lipase, Novozyme®-435, diastereoselectivity, azido-spironucleosides
Organisations: Chemistry

Identifiers

Local EPrints ID: 383085
URI: http://eprints.soton.ac.uk/id/eprint/383085
ISSN: 0008-6215
PURE UUID: 79598b3c-1bfa-4c83-8290-5f6b923a4c95

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Date deposited: 22 Oct 2015 10:28
Last modified: 14 Mar 2024 21:39

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Contributors

Author: Manish Kumar
Author: Vivek K. Sharma
Author: Rajesh Kumar
Author: Ashok K. Prasad

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