TY - JOUR

T1 - Problems of the Synthesis of Oligonucleotide Derivatives in the Realization of the Anchimeric Effect

AU - Dyudeeva, E. S.

AU - Pavlova, A. S.

AU - Kupryushkin, M. S.

AU - Pyshnyi, D. V.

AU - Pyshnaya, I. A.

N1 - Funding Information: The work on the analysis and implementation of the anchimeric effect was supported by the Russian Foundation for Basic Research (project no. 19-34-90132) and is a continuation of pilot studies on mass spectrometry analysis supported by the Russian Science Foundation in 2019 (project no. 18-14-00357). Publisher Copyright: © 2021, Pleiades Publishing, Ltd. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/3

Y1 - 2021/3

N2 - It has been found that the presence of a free OH group at the 3'-terminal residue of the substituted ethylene glycol fragment in a phosphoryl guanidine oligodeoxyribonucleotide derivative is a factor that determines the instability of the structure of the target oligonucleotide product under the conditions of a standard deblocking protocol. It has been shown that the main by-products of the realization of the anchimeric effect of the OH group are the products of the transesterification of the phosphoryl guanidine (PG) unit carrying the O-substituted ethylene glycol residue. The data of the mass spectrometry analysis indicate that, under alkaline conditions, the accumulation of derivatives devoid of the N,N,N',N'-substituted guanidine residue (1,3-dimethylimidazolidin-2-imine, DMI) or the entire 3'-terminal PG-containing nonnucleotide unit occurs.

AB - It has been found that the presence of a free OH group at the 3'-terminal residue of the substituted ethylene glycol fragment in a phosphoryl guanidine oligodeoxyribonucleotide derivative is a factor that determines the instability of the structure of the target oligonucleotide product under the conditions of a standard deblocking protocol. It has been shown that the main by-products of the realization of the anchimeric effect of the OH group are the products of the transesterification of the phosphoryl guanidine (PG) unit carrying the O-substituted ethylene glycol residue. The data of the mass spectrometry analysis indicate that, under alkaline conditions, the accumulation of derivatives devoid of the N,N,N',N'-substituted guanidine residue (1,3-dimethylimidazolidin-2-imine, DMI) or the entire 3'-terminal PG-containing nonnucleotide unit occurs.

KW - anchimeric effect

KW - mass spectrometry

KW - modified oligonucleotides

KW - phosphoryl guanidines

UR - http://www.scopus.com/inward/record.url?scp=85104860584&partnerID=8YFLogxK

U2 - 10.1134/S1068162021020096

DO - 10.1134/S1068162021020096

M3 - Article

AN - SCOPUS:85104860584

VL - 47

SP - 505

EP - 513

JO - Russian Journal of Bioorganic Chemistry

JF - Russian Journal of Bioorganic Chemistry

SN - 1068-1620

IS - 2

ER -