Total synthesis of amphidinolide E and amphidinolide E stereoisomers

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• 作者：Porino Va ; William R. Roush
• 关键词：Amphidinolide E stereoisomers ; [3+2] Annulation reaction ; Esterification of Fe(CO)₃-complexed dienoic acid
• 刊名：Tetrahedron
• 出版年：2007
• 出版时间：25 June 2007
• 年：2007
• 卷：63
• 期：26
• 页码：5768-5796
• 全文大小：1104 K

文摘

Four amphidinolide E stereoisomers, amphidinolide E (1), 2-epi-amphidinolide E (2), 19-epi-amphidinolide E (3), and 2-epi-19-epi-amphidinolide E (4), have been synthesized via the judicious union of aldehyde 5, allylsilanes 7 or 8, acids 9 or 10, and vinylstannane 6. The C19 stereocenters of the C19 epimeric allylsilanes 7 and 8 were introduced via crotylboration reactions early in the synthesis. [3+2] Annulation reactions of aldehyde 5 with allylsilanes 7 and 8 were employed to set the core tetrahydrofuran units of 1–4. Finally, the C2 stereocenter was installed by esterification using acid 9, without incident, or with acid 10, in which case an unexpected and completely stereoselective inversion of C2 occurs.