Synthesis of Some Trifluoromethylated Cyclodextrin Derivatives and Analysis of Their Properties as Artificial Glycosidases and Oxidases.

Jeannette Bjerre; Thomas Hauch Fenger; Lavinia Georgeta Marinescu; Mikael Bols

doi:10.1002/ejoc.200600762

Synthesis of Some Trifluoromethylated Cyclodextrin Derivatives and Analysis of Their Properties as Artificial Glycosidases and Oxidases.

Jeannette Bjerre, Thomas Hauch Fenger, Lavinia Georgeta Marinescu, Mikael Bols

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

54 Citationer (Scopus)

Abstract

Udgivelsesdato: 27/11-2006

Originalsprog	Engelsk
Tidsskrift	European Journal of Organic Chemistry
Vol/bind	4
Sider (fra-til)	704-710
Antal sider	7
ISSN	1434-193X
DOI	https://doi.org/10.1002/ejoc.200600762
Status	Udgivet - 2007
Udgivet eksternt	Ja

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10.1002/ejoc.200600762

http://www3.interscience.wiley.com/cgi-bin/fulltext/113489133/PDFSTART

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Citationsformater

@article{b5b9f89087b011dcbee902004c4f4f50,

title = "Synthesis of Some Trifluoromethylated Cyclodextrin Derivatives and Analysis of Their Properties as Artificial Glycosidases and Oxidases.",

abstract = "Cyclodextrin derivatives containing trifluoromethyl groups at C6 of the A and D rings were synthesized for the purpose of creating artificial enzymes. The compounds were synthesized by perbenzylation of beta-cyclodextrin followed by selective A,D-debenzylation according to Sina{\"y}. Subsequent oxidation to dialdehyde with Dess-Martin periodinane followed by addition of CF3 by using Arduengo carbene and TMSCF3 led to the C6-bistrifluoromethylated alcohols. These were either deprotected by hydrogenolysis or subjected to another round of oxidation to provide the corresponding ketones that were deprotected. The trifluoromethylated alcohols were found to be weak artificial enzymes catalysing hydrolysis of nitrophenyl glycosides at neutral pH with a kcat/kuncat of up to 56. It is proposed that this catalysis is analogues to the catalysis performed by related cyanohydrins. The trifluoro ketones were likewise weak articial enzymes catalysing oxidation of amines to nitro derivatives or alcohols to ketones with a kcat/kuncat of up to 133.",

author = "Jeannette Bjerre and {Hauch Fenger}, Thomas and {Georgeta Marinescu}, Lavinia and Mikael Bols",

year = "2007",

doi = "10.1002/ejoc.200600762",

language = "English",

volume = "4",

pages = "704--710",

journal = "European Journal of Organic Chemistry",

issn = "1434-193X",

publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",

}

TY - JOUR

T1 - Synthesis of Some Trifluoromethylated Cyclodextrin Derivatives and Analysis of Their Properties as Artificial Glycosidases and Oxidases.

AU - Bjerre, Jeannette

AU - Hauch Fenger, Thomas

AU - Georgeta Marinescu, Lavinia

AU - Bols, Mikael

PY - 2007

Y1 - 2007

N2 - Cyclodextrin derivatives containing trifluoromethyl groups at C6 of the A and D rings were synthesized for the purpose of creating artificial enzymes. The compounds were synthesized by perbenzylation of beta-cyclodextrin followed by selective A,D-debenzylation according to Sinaÿ. Subsequent oxidation to dialdehyde with Dess-Martin periodinane followed by addition of CF3 by using Arduengo carbene and TMSCF3 led to the C6-bistrifluoromethylated alcohols. These were either deprotected by hydrogenolysis or subjected to another round of oxidation to provide the corresponding ketones that were deprotected. The trifluoromethylated alcohols were found to be weak artificial enzymes catalysing hydrolysis of nitrophenyl glycosides at neutral pH with a kcat/kuncat of up to 56. It is proposed that this catalysis is analogues to the catalysis performed by related cyanohydrins. The trifluoro ketones were likewise weak articial enzymes catalysing oxidation of amines to nitro derivatives or alcohols to ketones with a kcat/kuncat of up to 133.

AB - Cyclodextrin derivatives containing trifluoromethyl groups at C6 of the A and D rings were synthesized for the purpose of creating artificial enzymes. The compounds were synthesized by perbenzylation of beta-cyclodextrin followed by selective A,D-debenzylation according to Sinaÿ. Subsequent oxidation to dialdehyde with Dess-Martin periodinane followed by addition of CF3 by using Arduengo carbene and TMSCF3 led to the C6-bistrifluoromethylated alcohols. These were either deprotected by hydrogenolysis or subjected to another round of oxidation to provide the corresponding ketones that were deprotected. The trifluoromethylated alcohols were found to be weak artificial enzymes catalysing hydrolysis of nitrophenyl glycosides at neutral pH with a kcat/kuncat of up to 56. It is proposed that this catalysis is analogues to the catalysis performed by related cyanohydrins. The trifluoro ketones were likewise weak articial enzymes catalysing oxidation of amines to nitro derivatives or alcohols to ketones with a kcat/kuncat of up to 133.

U2 - 10.1002/ejoc.200600762

DO - 10.1002/ejoc.200600762

M3 - Journal article

SN - 1434-193X

VL - 4

SP - 704

EP - 710

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

ER -