Study on the mechanism of diazomethane degradation of the sugar – aglycone linkage in gypsogenin 3-O-glycoside

✍ Scribed by Higuchi, Ryuichi ;Tokimitsu, Yoshinori ;Komori, Tetsuya

• Publisher: John Wiley and Sons
• Year: 1988
• Tongue: English
• Weight: 727 KB
• Volume: 1988
• Category: Article
• ISSN: 0947-3440
• DOI: 10.1002/jlac.198819880312

✦ Synopsis

Thc nicchanism of the diazomethane degradation of thc sugaraglycone linkage of the gypsogenin 3-0-glycoside (1) was studied. Since there are three kinds of funclional groups in 1the 4a-aldehyde group in the aglycone. the carboxy, and the 4'hydroxy group in the glucuronic acidwhich are presumed to contribute to the degradation reaction, the role of cach functional group was examincd using synthesized model compounds. As a rcsult of thc study, only thc 4a-aldehyde group was shown to be csscntial. By taking the above cvidcncc and the reaction of the aldehyde with diazomethane into account, the degradation is thought to proceed through an epoxide intermediate as shown in Scheme 6. The reaciion of gypsogenin with diazomethane was also examined.

As described in the preceding paper 2), gypsogenin 3-0glycoside (1) was treated with diazomethanelether in methanol to give an aglycone (4), sugars (2 and 3), and an unknown compound (5) by cleavage of the sugaraglycone Scheme 1

OR' HO +@Me