Catalytic diastereoselective polycyclization of homo(polyprenyl)arene analogues bearing terminal siloxyvinyl groups.
Highly diastereoselective polycyclization of homo(polyprenyl)arene analogues bearing terminal siloxyvinyl groups was catalyzed by tin(IV) chloride (10 mol %). The cyclizations of tert-butyldiphenylsilyl and triisopropylsilyl polyenol ethers gave 4alpha(equatorial)- and 4beta(axial)-siloxypolycycles as major isomers, respectively. The strong nucleophilicity of pro-C(9), a (6E) geometry, and a bulky silyl group effectively favored the alpha-preference, whereas the weak nucleophilicity of pro-C(9), a (6Z)-geometry, and less steric hindrance of a silyl group favored the beta-preference. [reaction: see text].
Uyanik
Muhammet
M
Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan.
Ishihara
Kazuaki
K
Yamamoto
Hisashi
H
D002384:Catalysis; D003500:Cyclization; D013237:Stereoisomerism; D013729:Terpenes / Q000138:chemical synthesis*; D017971:Tin Compounds / Q000737:chemistry
D013729:Terpenes; D017971:Tin Compounds; C023599:stannous chloride