An efficient and highly enantioselective synthesis of tipranavir is realized based on an iridium-catalyzed asymmetric allylic substitution. High yield and diastereoselectivity (>20:1), as well as excellent enantioselectivity (99% ee), were obtained for the key intermediate through direct asymmetric alkylation reaction of dihydropyranone with allylic tert-butyl carbonate. Anti-AIDS drug of tipranavir was finally accomplished in 8 steps and 6 pots starting from commercially available 1-phenyl-3-hexanone in 20.7% overall yield with 99% ee and >20:1 dr.

中文翻译：

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基于铱催化的二氢吡喃酮不对称烯丙基取代替拉那韦的全合成


基于铱催化的不对称烯丙基取代实现了替拉那韦的高效且高度对映选择性合成。通过二氢吡喃酮与烯丙基叔丁基碳酸酯的直接不对称烷基化反应，关键中间体获得了高产率和非对映选择性 （>20：1） 以及优异的对映选择性 （99% ee）。替拉那韦的抗艾滋病药物最终以 8 个步骤和 6 罐完成，从市售的 1-苯基-3-己酮开始，总产率为 20.7%，ee为 99%，%为 >20：1 dr。