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Chemistry of Tonghaosu Analogs: Novel Acid‐Catalyzed Nucleophilic Addition to the Dienyl Acetal System
Author(s) -
Yin BiaoLin,
Wu WenMin,
Hu TaiShan,
Wu YuLin
Publication year - 2003
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200300343
Subject(s) - chemistry , nucleophile , acetal , adduct , enol , organic chemistry , reagent , catalysis , nucleophilic addition , medicinal chemistry , ether
The acid‐catalyzed nucleophilic addition reaction of spiroketal enol ether‐containing tonghaosu analogs 2 was explored. Soft nucleophiles, such as mercaptans, alcohols and heteroaromatic compounds, gave rise exclusively to 1,6‐adducts, while harder nucleophiles, such as Grignard reagents, afforded mixtures of 1,2‐ and 1,6‐adducts. The reaction with cysteine and glutathione, which might be related to the mode of action of insect antifeeding, also took place smoothly. Friedel−Crafts dimerization reactions of 10 and 11 gave the dimers 12 and 13 respectively. By comparison of 1 H NMR spectroscopic data, we also suggest that the structure of compound 9 reported in the literature for a natural product is revised to that of compound 13 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)