Bifunctional chiral dehydroalanines for peptide coupling and stereoselective S-Michael addition

Marta I. Gutiérrez-Jiménez; Carlos Aydillo; Claudio D. Navo; Alberto Avenoza; Francisco Corzana; Gonzalo Jiménez-Osés; María M. Zurbano; Jesús H. Busto; Jesús M. Peregrina

doi:10.1021/acs.orglett.6b00840

Bifunctional chiral dehydroalanines for peptide coupling and stereoselective S-Michael addition

Marta I. Gutiérrez-Jiménez, Carlos Aydillo, Claudio D. Navo, Alberto Avenoza, Francisco Corzana, Gonzalo Jiménez-Osés, María M. Zurbano, Jesús H. Busto, Jesús M. Peregrina

Department of Chemistry

16 Citations (Scopus)

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Abstract

A second generation of chiral bicyclic dehydroalanines easily accessible from serine has been developed. These scaffolds behaved as excellent S-Michael acceptors when tri-O-acetyl-2-acetamido-2-deoxy-1-thio-α-d-galactopyranose (abbreviated as GalNAc-α-SH) was used as a nucleophile. This addition proceeds with total chemo- and stereoselectivity, complete atom economy, quickly, and at room temperature, making it a true click reaction. The Michael adducts were easily transformed into S-(2-acetamido-2-deoxy-α-d-galactopyranosyl)-l- and -d-cysteines, which can be regarded as mimics of the Tn antigen derived from l-Ser (α-d-GalNAc-l-Ser) and d-Ser (α-d-GalNAc-d-Ser), respectively.

Original language	English
Journal	Organic Letters
Volume	18
Issue number	12
Pages (from-to)	2796-2799
Number of pages	4
ISSN	1523-7060
DOIs	https://doi.org/10.1021/acs.orglett.6b00840
Publication status	Published - 17 Jun 2016

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@article{9452c622f524499881a91e66e026c90f,

title = "Bifunctional chiral dehydroalanines for peptide coupling and stereoselective S-Michael addition",

abstract = "A second generation of chiral bicyclic dehydroalanines easily accessible from serine has been developed. These scaffolds behaved as excellent S-Michael acceptors when tri-O-acetyl-2-acetamido-2-deoxy-1-thio-α-d-galactopyranose (abbreviated as GalNAc-α-SH) was used as a nucleophile. This addition proceeds with total chemo- and stereoselectivity, complete atom economy, quickly, and at room temperature, making it a true click reaction. The Michael adducts were easily transformed into S-(2-acetamido-2-deoxy-α-d-galactopyranosyl)-l- and -d-cysteines, which can be regarded as mimics of the Tn antigen derived from l-Ser (α-d-GalNAc-l-Ser) and d-Ser (α-d-GalNAc-d-Ser), respectively.",

author = "Guti{\'e}rrez-Jim{\'e}nez, {Marta I.} and Carlos Aydillo and Navo, {Claudio D.} and Alberto Avenoza and Francisco Corzana and Gonzalo Jim{\'e}nez-Os{\'e}s and Zurbano, {Mar{\'i}a M.} and Busto, {Jes{\'u}s H.} and Peregrina, {Jes{\'u}s M.}",

year = "2016",

month = jun,

day = "17",

doi = "10.1021/acs.orglett.6b00840",

language = "English",

volume = "18",

pages = "2796--2799",

journal = "Organic Letters",

issn = "1523-7060",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Bifunctional chiral dehydroalanines for peptide coupling and stereoselective S-Michael addition

AU - Gutiérrez-Jiménez, Marta I.

AU - Aydillo, Carlos

AU - Navo, Claudio D.

AU - Avenoza, Alberto

AU - Corzana, Francisco

AU - Jiménez-Osés, Gonzalo

AU - Zurbano, María M.

AU - Busto, Jesús H.

AU - Peregrina, Jesús M.

PY - 2016/6/17

Y1 - 2016/6/17

N2 - A second generation of chiral bicyclic dehydroalanines easily accessible from serine has been developed. These scaffolds behaved as excellent S-Michael acceptors when tri-O-acetyl-2-acetamido-2-deoxy-1-thio-α-d-galactopyranose (abbreviated as GalNAc-α-SH) was used as a nucleophile. This addition proceeds with total chemo- and stereoselectivity, complete atom economy, quickly, and at room temperature, making it a true click reaction. The Michael adducts were easily transformed into S-(2-acetamido-2-deoxy-α-d-galactopyranosyl)-l- and -d-cysteines, which can be regarded as mimics of the Tn antigen derived from l-Ser (α-d-GalNAc-l-Ser) and d-Ser (α-d-GalNAc-d-Ser), respectively.

AB - A second generation of chiral bicyclic dehydroalanines easily accessible from serine has been developed. These scaffolds behaved as excellent S-Michael acceptors when tri-O-acetyl-2-acetamido-2-deoxy-1-thio-α-d-galactopyranose (abbreviated as GalNAc-α-SH) was used as a nucleophile. This addition proceeds with total chemo- and stereoselectivity, complete atom economy, quickly, and at room temperature, making it a true click reaction. The Michael adducts were easily transformed into S-(2-acetamido-2-deoxy-α-d-galactopyranosyl)-l- and -d-cysteines, which can be regarded as mimics of the Tn antigen derived from l-Ser (α-d-GalNAc-l-Ser) and d-Ser (α-d-GalNAc-d-Ser), respectively.

U2 - 10.1021/acs.orglett.6b00840

DO - 10.1021/acs.orglett.6b00840

M3 - Letter

C2 - 27246362

SN - 1523-7060

VL - 18

SP - 2796

EP - 2799

JO - Organic Letters

JF - Organic Letters

IS - 12

ER -

Bifunctional chiral dehydroalanines for peptide coupling and stereoselective S-Michael addition

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