Site-Selective Dehydroxy-Chlorination of Secondary Alcohols in Unprotected Glycosides

Ji Zhang; Niels R M Reintjens; Jayaraman Dhineshkumar; Martin D Witte; Adriaan J Minnaard

doi:10.1021/acs.orglett.2c01992

Site-Selective Dehydroxy-Chlorination of Secondary Alcohols in Unprotected Glycosides

Ji Zhang, Niels R M Reintjens, Jayaraman Dhineshkumar, Martin D Witte^*, Adriaan J Minnaard^*

^*Corresponding author for this work

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

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Abstract

To circumvent protecting groups, the site-selective modification of unprotected glycosides is intensively studied. We show that site-selective oxidation, followed by treatment of the corresponding trityl hydrazone with tert-butyl hypochlorite and a H atom donor provides an effective way to introduce a chloride substituent in a variety of mono- and disaccharides. The stereoselectivity can be steered, and a new geminal dichlorination reaction is described as well. This strategy challenges existing methods that lead to overchlorination.

Original language	English
Pages (from-to)	5339-5344
Number of pages	6
Journal	Organic letters
Volume	24
Issue number	29
Early online date	17-Jul-2022
DOIs	https://doi.org/10.1021/acs.orglett.2c01992
Publication status	Published - 29-Jul-2022

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Site-Selective Dehydroxy-Chlorination of Secondary Alcohols in Unprotected GlycosidesFinal publisher's version, 1.64 MBLicence: CC BY

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CCDC 2150551: Experimental Crystal Structure Determination
Zhang, J. (Contributor), Reintjens, N. (Contributor), Jayaraman, D. (Contributor), Witte, M. D. (Contributor) & Minnaard, A. J. (Contributor), Cambridge Crystallographic Data Centre, 7-Feb-2022
DOI: 10.5517/ccdc.csd.cc2b5tmz
Dataset
CCDC 2150550: Experimental Crystal Structure Determination
Zhang, J. (Contributor), Reintjens, N. (Contributor), Jayaraman, D. (Contributor), Witte, M. D. (Contributor) & Minnaard, A. J. (Contributor), Cambridge Crystallographic Data Centre, 7-Feb-2022
DOI: 10.5517/ccdc.csd.cc2b5tly
Dataset
CCDC 2150508: Experimental Crystal Structure Determination
Zhang, J. (Contributor), Reintjens, N. (Contributor), Jayaraman, D. (Contributor), Witte, M. D. (Contributor) & Minnaard, A. J. (Contributor), Cambridge Crystallographic Data Centre, 7-Feb-2022
DOI: 10.5517/ccdc.csd.cc2b5s7k
Dataset

Cite this

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title = "Site-Selective Dehydroxy-Chlorination of Secondary Alcohols in Unprotected Glycosides",

abstract = "To circumvent protecting groups, the site-selective modification of unprotected glycosides is intensively studied. We show that site-selective oxidation, followed by treatment of the corresponding trityl hydrazone with tert-butyl hypochlorite and a H atom donor provides an effective way to introduce a chloride substituent in a variety of mono- and disaccharides. The stereoselectivity can be steered, and a new geminal dichlorination reaction is described as well. This strategy challenges existing methods that lead to overchlorination.",

author = "Ji Zhang and Reintjens, {Niels R M} and Jayaraman Dhineshkumar and Witte, {Martin D} and Minnaard, {Adriaan J}",

year = "2022",

month = jul,

day = "29",

doi = "10.1021/acs.orglett.2c01992",

language = "English",

volume = "24",

pages = "5339--5344",

journal = "Organic letters",

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T1 - Site-Selective Dehydroxy-Chlorination of Secondary Alcohols in Unprotected Glycosides

AU - Zhang, Ji

AU - Reintjens, Niels R M

AU - Dhineshkumar, Jayaraman

AU - Witte, Martin D

AU - Minnaard, Adriaan J

PY - 2022/7/29

Y1 - 2022/7/29

N2 - To circumvent protecting groups, the site-selective modification of unprotected glycosides is intensively studied. We show that site-selective oxidation, followed by treatment of the corresponding trityl hydrazone with tert-butyl hypochlorite and a H atom donor provides an effective way to introduce a chloride substituent in a variety of mono- and disaccharides. The stereoselectivity can be steered, and a new geminal dichlorination reaction is described as well. This strategy challenges existing methods that lead to overchlorination.

AB - To circumvent protecting groups, the site-selective modification of unprotected glycosides is intensively studied. We show that site-selective oxidation, followed by treatment of the corresponding trityl hydrazone with tert-butyl hypochlorite and a H atom donor provides an effective way to introduce a chloride substituent in a variety of mono- and disaccharides. The stereoselectivity can be steered, and a new geminal dichlorination reaction is described as well. This strategy challenges existing methods that lead to overchlorination.

U2 - 10.1021/acs.orglett.2c01992

DO - 10.1021/acs.orglett.2c01992

M3 - Article

C2 - 35848103

SN - 1523-7060

VL - 24

SP - 5339

EP - 5344

JO - Organic letters

JF - Organic letters

IS - 29

ER -

Site-Selective Dehydroxy-Chlorination of Secondary Alcohols in Unprotected Glycosides

Abstract

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Datasets

CCDC 2150551: Experimental Crystal Structure Determination

CCDC 2150550: Experimental Crystal Structure Determination

CCDC 2150508: Experimental Crystal Structure Determination

Cite this