Stereospecific Access to Bridged [n.2.1] Skeletons Through Gold-Catalyzed Tandem Reaction of Indolyl Homopropargyl Amides

An efficient gold-catalyzed anti-Markovnikov cycloisomerization-initiated tandem reaction of Boc-protected indole tethered homopropargyl amides has been achieved. This method delivers a wide range of valuable bridged aza-[n.2.1] skeletons (n =3–7) at room temperature with high diastereoselectivity and enantioselectivity by a chirality-transfer strategy. Moreover, the gold-catalyzed tandem reaction of homopropargyl alcohol is also achieved to produce the bridged oxa-[3.2.1] skeleton.