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Stereoselective synthesis of UDP-2-(2-ketopropyl)galactose aided by di-tert-butylsilylene protecting group

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Abstract

UDP-2-(2-ketopropyl)galactose (1) has been utilized as a valuable probe for profiling proteins modified by O-GlcNAc. In this work, we developed a protocol for efficient synthesis of 1. Thus, 2-methallylgalactose derivative 11, a synthetic intermediate for the compound 1, was prepared by stereoselective iodination and methallylation at C-2 position, through exploitation of 4,6-O-di-tert-butylsilylene protecting group.

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Scheme 1
Scheme 2
Scheme 3

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Abbreviations

AIBN:

α,α′-azobisisobutyronitrile

DMF:

N,N-dimethylformamide

DTBS:

di-tert-butylsilylene

ESI:

electrospray ionization

GalT:

β-1,4-galactosyltransferase

NIS:

N-iodosuccinimide

OGA:

O-linked β-N-acetylglucosamine hydrolase

O-GlcNAc:

O-linked β-N-acetylglucosamine

OGT:

O-linked β-N-acetylglucosamine transferase

PEG:

polyethylene glycol

Py:

pyridine

THF:

tetrahydrofuran

UDP:

uridine diphosphate

UMP:

uridine monophosphate

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Acknowledgments

We thank Dr. Yayoi Hongo and Dr. Takemichi Nakamura for ESI mass measurements. We also thank Ms. Akemi Takahashi and Ms. Satoko Shirahata for technical assistance. This research was supported by the Advanced Research for Medical Products Mining Program (09–01) of the National Institute of Biomedical Innovation, Osaka, Japan (NIBIO).

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Authors and Affiliations

  1. Synthetic Cellular Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan

    Yasuharu Sakamoto, Tsuyoshi Ohta & Yukishige Ito

  2. Japan Science and Technology Agency (JST), ERATO Glycotrilogy Project, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan

    Yukishige Ito

Authors
  1. Yasuharu Sakamoto
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  2. Tsuyoshi Ohta
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  3. Yukishige Ito
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Correspondence to Yasuharu Sakamoto or Yukishige Ito.

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Sakamoto, Y., Ohta, T. & Ito, Y. Stereoselective synthesis of UDP-2-(2-ketopropyl)galactose aided by di-tert-butylsilylene protecting group. Glycoconj J 32, 541–548 (2015). https://doi.org/10.1007/s10719-015-9581-y

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