Laboratorium für Organische Chemie, HCI H335, Eidgenössische Technische Hochschule Zürich, Vladimir-Prelog-Weg 3, 8093 Zürich (Switzerland).
Angew Chem Int Ed Engl. 2015 Nov 23;54(48):14363-7. doi: 10.1002/anie.201506933. Epub 2015 Oct 2.
Fully stereodivergent dual-catalytic α-allylation of protected α-amino- and α-hydroxyacetaldehydes is achieved through iridium- and amine-catalyzed substitution of racemic allylic alcohols with chiral enamines generated in situ. The operationally simple method furnishes useful aldehyde building blocks in good yields, more than 99% ee, and with d.r. values greater than 20:1 in some cases. Additionally, the γ,δ-unsaturated products can be further functionalized in a stereodivergent fashion with high selectivity and with preservation of stereochemical integrity at the Cα position.
通过手性烯胺原位生成的手性亚胺与外消旋烯丙醇进行铱和胺催化取代，实现了保护的α-氨基-和α-羟基乙醛的完全立体发散双催化α-烯丙基化。该操作简单的方法以良好的收率、超过 99%的对映体过量值和在某些情况下大于 20:1 的 d.r. 值提供了有用的醛砌块。此外，γ，δ-不饱和产物可以以高选择性进一步进行立体发散官能化，并且在 Cα 位置保持立体化学完整性。
