226910-55-0Relevant articles and documents
Enantioselective total synthesis of (+)-taxusin
Hara, Ryoma,Furukawa, Takashi,Kashima, Hajime,Kusama, Hiroyuki,Horiguchi, Yoshiaki,Kuwajima, Isao
, p. 3072 - 3082 (1999)
For the total synthesis of (+)-taxusin, the AC-ring fragment 8 was prepared from an optically active 2-bromo-3-siloxycyclohexenecarbacetal 5 via 4 steps and was converted to the dienol silyl ether 13. The thus-obtained 13 underwent B-ring cyclization in the presence of Me2AlOTf to produce the ABC endo-tricarbocycle 14 having C9α, C10β-substituents, which was converted to the cyclopropyl ketone 21a. Introduction of C19 methyl via reductive cleavage of the cyclopropane ring under Birch conditions and successive in situ treatment of the resulting enol with methanol gave the C3α-protonated ketone 24. Next, 24 was converted to the allylsilane 29, which was then oxidized with m-CPBA to produce the fully functionalized taxusin carbon skeleton. Finally, removal of the silyl protecting groups followed by acetylation completed the total synthesis of (+)-taxusin.