Syntheses of T N building blocks N α-(9-fluorenylmethoxycarbonyl)- O-(3,4,6-tri- O-acetyl-2-azido-2-deoxy-α- d-galactopyranosyl)- l-serine/ l-threonine pentafluorophenyl esters: comparison of protocols and elucidation of side reactions
[Display omitted] T N antigen building blocks N α-(9-fluorenylmethoxycarbonyl)- O-(3,4,6-tri- O-acetyl-2-azido-2-deoxy-α- d-galactopyranosyl)- l-serine/ l-threonine pentafluorophenyl ester [Fmoc- l-Ser/ l-Thr(Ac 3-α- d-GalN 3)-OPfp, 13/ 14] have been synthesized by two different routes, which have b...
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Published in | Carbohydrate research Vol. 340; no. 7; pp. 1273 - 1285 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
Elsevier Ltd
23.05.2005
|
Subjects | |
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Abstract | [Display omitted]
T
N antigen building blocks
N
α-(9-fluorenylmethoxycarbonyl)-
O-(3,4,6-tri-
O-acetyl-2-azido-2-deoxy-α-
d-galactopyranosyl)-
l-serine/
l-threonine pentafluorophenyl ester [Fmoc-
l-Ser/
l-Thr(Ac
3-α-
d-GalN
3)-OPfp,
13/
14] have been synthesized by two different routes, which have been compared. Overall isolated yields [three or four chemical steps, and minimal intermediary purification steps] of enantiopure
13 and
14 were 5–18% and 6–10%, respectively, based on 3,4,6-tri-
O-acetyl-
d-galactal (
1). A byproduct of the initial azidonitration reaction of the synthetic sequence, that is,
N-acetyl-3,4,6-tri-
O-acetyl-2-azido-2-deoxy-α-
d-galactopyranosylamine (
5), has been characterized by X-ray crystallography, and shown by
1H NMR spectroscopy to form complexes with lithium bromide, lithium iodide, or sodium iodide in acetonitrile-
d
3. Intermediates 3,4,6-tri-
O-acetyl-2-azido-2-deoxy-α-
d-galactopyranosyl bromide (
6) and 3,4,6-tri-
O-acetyl-2-azido-2-deoxy-β-
d-galactopyranosyl chloride (
7) were used to glycosylate
N
α-(9-fluorenylmethoxycarbonyl)-
l-serine/
l-threonine pentafluorophenyl esters [Fmoc-
l-Ser/
l-Thr-OPfp,
11/
12]. Previously undescribed low-level dehydration side reactions were observed at this stage; the unwanted byproducts were easily removed by column chromatography. |
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AbstractList | [Display omitted]
T
N antigen building blocks
N
α-(9-fluorenylmethoxycarbonyl)-
O-(3,4,6-tri-
O-acetyl-2-azido-2-deoxy-α-
d-galactopyranosyl)-
l-serine/
l-threonine pentafluorophenyl ester [Fmoc-
l-Ser/
l-Thr(Ac
3-α-
d-GalN
3)-OPfp,
13/
14] have been synthesized by two different routes, which have been compared. Overall isolated yields [three or four chemical steps, and minimal intermediary purification steps] of enantiopure
13 and
14 were 5–18% and 6–10%, respectively, based on 3,4,6-tri-
O-acetyl-
d-galactal (
1). A byproduct of the initial azidonitration reaction of the synthetic sequence, that is,
N-acetyl-3,4,6-tri-
O-acetyl-2-azido-2-deoxy-α-
d-galactopyranosylamine (
5), has been characterized by X-ray crystallography, and shown by
1H NMR spectroscopy to form complexes with lithium bromide, lithium iodide, or sodium iodide in acetonitrile-
d
3. Intermediates 3,4,6-tri-
O-acetyl-2-azido-2-deoxy-α-
d-galactopyranosyl bromide (
6) and 3,4,6-tri-
O-acetyl-2-azido-2-deoxy-β-
d-galactopyranosyl chloride (
7) were used to glycosylate
N
α-(9-fluorenylmethoxycarbonyl)-
l-serine/
l-threonine pentafluorophenyl esters [Fmoc-
l-Ser/
l-Thr-OPfp,
11/
12]. Previously undescribed low-level dehydration side reactions were observed at this stage; the unwanted byproducts were easily removed by column chromatography. |
Author | Barany, George Young, Victor G. Live, David Lohani, Sachin Liu, Mian |
Author_xml | – sequence: 1 givenname: Mian surname: Liu fullname: Liu, Mian organization: Department of Biochemistry, Molecular Biology and Biophysics, University of Minnesota, Minneapolis, MN 55455, USA – sequence: 2 givenname: Victor G. surname: Young fullname: Young, Victor G. organization: Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA – sequence: 3 givenname: Sachin surname: Lohani fullname: Lohani, Sachin organization: Department of Pharmaceutics, University of Minnesota, Minneapolis, MN 55455, USA – sequence: 4 givenname: David surname: Live fullname: Live, David email: david@nmr1.biochem.umn.edu organization: Department of Biochemistry, Molecular Biology and Biophysics, University of Minnesota, Minneapolis, MN 55455, USA – sequence: 5 givenname: George surname: Barany fullname: Barany, George email: barany@umn.edu organization: Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA |
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Keywords | Side reactions Glycosylation Z-Dehydrothreonine Dehydroalanine Metal ion–carbohydrate complexes Glycopeptide synthetic building blocks |
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References | Peters, Bielfeldt, Meldal, Bock, Paulsen (bib8) 1992; 9 Yano, Mikata (bib24) 2002; 75 Verchère, Chapelle, Xin, Crans (bib23) 1998; 47 Srinivas, Muktha, Radhika, Guru Row, Jayaraman (bib19) 2004; 339 Angyal (bib21) 1973; 35 Van den Steen, Rudd, Dwek, Opdenakker (bib1) 1998; 33 Hojo, Nakahara (bib5) 2000; 1 Paulsen, Richter, Sinnwell, Stenzel (bib17) 1978; 64 Kunz, Birnbach (bib15) 1986; 25 Somlai, Lovas, Forgó, Murphy, Penke (bib25) 2001; 31 Liu, Live, Barany (bib12) 2004; 22 Kunz (bib2) 1987; 26 Lemieux, Ratcliffe (bib13) 1979; 57 Rendleman (bib20) 1966; 21 Jansson, Meldal, Bock (bib26) 1992; 13 Paulsen, Bielfeldt, Peters, Meldal, Bock (bib9) 1994; 4 Bielfeldt, Peters, Meldal, Bock, Paulsen (bib6) 1992; 31 Yule, Wong, Gandhi, Qiu, Riopel, Koganty (bib10) 1995; 36 Broddefalk, Nilsson, Kihlberg (bib18) 1994; 13 SHELXTL V6.10, Bruker Analytical X-ray Systems, Madison, WI, 2000 Sames, Chen, Danishefsky (bib3) 1997; 389 Gururaja, Ramasubbu, Levine (bib11) 1996; 3 SAINT V6.2, Bruker analytical X-ray systems, Madison, WI, 2001 Kuduk, Schwarz, Chen, Glunz, Sames, Ragupathi, Livingston, Danishefsky (bib4) 1998; 120 Paulsen, Peters, Bielfedt, Meldal, Bock (bib16) 1995; 268 Blessing (bib28) 1995; 51 Lüning, Norberg, Tejbrant (bib7) 1989; 6 Vargas-Berenguel, Meldal, Paulsen, Bock (bib14) 1994; 18 Angyal (bib22) 1989; 47 |
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T
N antigen building blocks
N
α-(9-fluorenylmethoxycarbonyl)-
O-(3,4,6-tri-
O-acetyl-2-azido-2-deoxy-α-
d-galactopyranosyl)-
l-serine/... |
SourceID | elsevier |
SourceType | Publisher |
StartPage | 1273 |
SubjectTerms | Dehydroalanine Glycopeptide synthetic building blocks Glycosylation Metal ion–carbohydrate complexes Side reactions Z-Dehydrothreonine |
Title | Syntheses of T N building blocks N α-(9-fluorenylmethoxycarbonyl)- O-(3,4,6-tri- O-acetyl-2-azido-2-deoxy-α- d-galactopyranosyl)- l-serine/ l-threonine pentafluorophenyl esters: comparison of protocols and elucidation of side reactions |
URI | https://dx.doi.org/10.1016/j.carres.2005.02.029 |
Volume | 340 |
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