Abstract
AbstractGold carbene reactivity patterns were accessed by ynamide insertion into a C(sp3)H bond. A substantial increase in molecular complexity occurred through the cascade polycyclization of N‐allyl ynamides to form fused nitrogen‐heterocycle scaffolds. Exquisite selectivity was observed despite several competing pathways in an efficient gold‐catalyzed synthesis of densely functionalized C(sp3)‐rich polycycles and a copper‐catalyzed synthesis of fused pyridine derivatives. The respective gold–keteniminium and ketenimine activation pathways have been explored through a structure–reactivity study, and isotopic labeling identified turnover‐limiting CH bond‐cleavage in both processes.
Highlights
Access to molecules with stereogenic centers and a higher fraction of C(sp3) is increasingly desirable in pharmaceutical fragment design and lead discovery, as it is associated with improving chances of clinical success.[1]
Gold carbene reactivity patterns were accessed by ynamide insertion into a C(sp3)ÀH bond
The use of p-acid catalysis to generate metal–carbene character directly from triple bonds offers a rapid route to molecular complexity.[2]
Summary
Access to molecules with stereogenic centers and a higher fraction of C(sp3) is increasingly desirable in pharmaceutical fragment design and lead discovery, as it is associated with improving chances of clinical success.[1]. With reference to this strategy, a gold carbene was formed previously by the formal insertion of an ynamide into a CÀO s-bond (Scheme 1 b).[6,7] further cyclization was not observed.
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