Stereoselective synthesis of PEGylated azoles via 1,3-dipolar cycloaddition

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Stereoselective synthesis of PEGylated azoles via 1,3-dipolar cycloaddition. / Kazakova, Angelina V.; Konev, Alexander S.; Khlebnikov, Alexander F.

In: Tetrahedron, Vol. 77, 131774, 01.01.2021.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{0c9c221dc35e471a8ff0db6c04a6c463,

title = "Stereoselective synthesis of PEGylated azoles via 1,3-dipolar cycloaddition",

abstract = "Diastereoselective synthesis of PEGylated imidazolidines, oxazolidines, thiazolidines, pyrrolo[3,4-c]pyrroles and fulleropyrrolidines in high yields is reported. The 1,3-dipolar cycloaddition of azomethine ylides generated via thermal ring-opening of PEGylated aziridines to ketenimines, ketenes, thioketones, maleimides, DMAD and fullerene C60 was found to proceed under different conditions. The use of C[dbnd]O, C[dbnd]N and C[dbnd]S dipolarophiles requires more harsh reaction conditions, compared with C[dbnd]C and C[tbnd]C dipolarophiles, to suppress the side reaction of aziridine “dimerization”. The stereocontrol of the product configuration is achieved through stereospecificity of two consecutive concerted reactions: electrocyclic aziridine ring opening followed by 1,3-dipolar cycloaddition of the resulting azomethine ylide: only trans-adducts are formed from cis-aziridines, whereas trans-aziridines give exclusively cis-adducts. The structure and molecular-mass distribution of the resulting PEGylated heterocycles are exhaustively characterized by 1H, 13C NMR, IR and HRMS.",

keywords = "Aziridines, Azoles, Azomethine ylides, Polyethylene glycol, OXAZOLIDINES, THERMOLYSIS, THERAPY, AZOMETHINE YLIDES, CHEMISTRY, DERIVATIVES, HYDANTOIN, IMIDAZOLIDINES",

author = "Kazakova, {Angelina V.} and Konev, {Alexander S.} and Khlebnikov, {Alexander F.}",

note = "Funding Information: This work was financially supported by the Russian Science Foundation ( 19-13-00039 ). This research was performed using resources of the Centre for Magnetic Resonance and the Centre for Chemical Analysis and Materials of Research park of St. Petersburg State University, the assistance of the specialists of the research park is gratefully acknowledged. Publisher Copyright: {\textcopyright} 2020 Elsevier Ltd Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",

year = "2021",

month = jan,

day = "1",

doi = "10.1016/j.tet.2020.131774",

language = "English",

volume = "77",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - Stereoselective synthesis of PEGylated azoles via 1,3-dipolar cycloaddition

AU - Kazakova, Angelina V.

AU - Konev, Alexander S.

AU - Khlebnikov, Alexander F.

N1 - Funding Information: This work was financially supported by the Russian Science Foundation ( 19-13-00039 ). This research was performed using resources of the Centre for Magnetic Resonance and the Centre for Chemical Analysis and Materials of Research park of St. Petersburg State University, the assistance of the specialists of the research park is gratefully acknowledged. Publisher Copyright: © 2020 Elsevier Ltd Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2021/1/1

Y1 - 2021/1/1

N2 - Diastereoselective synthesis of PEGylated imidazolidines, oxazolidines, thiazolidines, pyrrolo[3,4-c]pyrroles and fulleropyrrolidines in high yields is reported. The 1,3-dipolar cycloaddition of azomethine ylides generated via thermal ring-opening of PEGylated aziridines to ketenimines, ketenes, thioketones, maleimides, DMAD and fullerene C60 was found to proceed under different conditions. The use of C[dbnd]O, C[dbnd]N and C[dbnd]S dipolarophiles requires more harsh reaction conditions, compared with C[dbnd]C and C[tbnd]C dipolarophiles, to suppress the side reaction of aziridine “dimerization”. The stereocontrol of the product configuration is achieved through stereospecificity of two consecutive concerted reactions: electrocyclic aziridine ring opening followed by 1,3-dipolar cycloaddition of the resulting azomethine ylide: only trans-adducts are formed from cis-aziridines, whereas trans-aziridines give exclusively cis-adducts. The structure and molecular-mass distribution of the resulting PEGylated heterocycles are exhaustively characterized by 1H, 13C NMR, IR and HRMS.

AB - Diastereoselective synthesis of PEGylated imidazolidines, oxazolidines, thiazolidines, pyrrolo[3,4-c]pyrroles and fulleropyrrolidines in high yields is reported. The 1,3-dipolar cycloaddition of azomethine ylides generated via thermal ring-opening of PEGylated aziridines to ketenimines, ketenes, thioketones, maleimides, DMAD and fullerene C60 was found to proceed under different conditions. The use of C[dbnd]O, C[dbnd]N and C[dbnd]S dipolarophiles requires more harsh reaction conditions, compared with C[dbnd]C and C[tbnd]C dipolarophiles, to suppress the side reaction of aziridine “dimerization”. The stereocontrol of the product configuration is achieved through stereospecificity of two consecutive concerted reactions: electrocyclic aziridine ring opening followed by 1,3-dipolar cycloaddition of the resulting azomethine ylide: only trans-adducts are formed from cis-aziridines, whereas trans-aziridines give exclusively cis-adducts. The structure and molecular-mass distribution of the resulting PEGylated heterocycles are exhaustively characterized by 1H, 13C NMR, IR and HRMS.

KW - Aziridines

KW - Azoles

KW - Azomethine ylides

KW - Polyethylene glycol

KW - OXAZOLIDINES

KW - THERMOLYSIS

KW - THERAPY

KW - AZOMETHINE YLIDES

KW - CHEMISTRY

KW - DERIVATIVES

KW - HYDANTOIN

KW - IMIDAZOLIDINES

UR - http://www.scopus.com/inward/record.url?scp=85096564884&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2020.131774

DO - 10.1016/j.tet.2020.131774

M3 - Article

AN - SCOPUS:85096564884

VL - 77

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

M1 - 131774

ER -

ID: 74411027