Tetrahydroquinolines constitute important structural features present in a number of biologically active alkaloids. Especially, 2-substituted tetrahydroquinoline has drawn medicinal chemists’ attention as a privileged structure. Angustureine, one member of 2-substituted tetrahydroquinoline alkaloids, was first isolated by JacquemondCollet and his co-workers in 1999 from Galipea officinalis, which has been used in traditional herbal medicine to treat a fever of dyspepsia, dysentery and chronic diarrhea. Recently, anti-tuberculous, anti-malarial, and cytotoxic activities have been reported for angustureine. In the context to develop efficient synthetic methods for diversity oriented synthesis of tetrahydroquinolines, herein, we report a concise synthesis of (+)-(S)-angustureine and hydroarylation strategy. As outlined in Figure 1, our synthetic stratagem includes the introduction of a chiral side chain by Mitsunobu reaction and the subsequent hydroarylation to dihydroquinoline. This approach is flexible and applicable to the preparation of other 2-substituted tetrahydroquinolines, as well. To this end, we chose the aniline as our starting point (Scheme 1). N-methanesulfonyl protection of aniline, followed by Mitsunobu inversion of the (R)-(+)1-octyn-3-ol (4) (98% ee) with the resulting methanesulfonanilide 3 in the presence of DEAD/PPh3, afforded Npropargylaniline 5. The Mesyl-NH group served as an efficient nucleophile for Mitsunobu reaction as well as an arene-free protecting group in the next hydroarylation step. With the hydroarylation precursor 5 in hand, we have explored the feasibility of intramolecular hydroarylation under a variety of catalytic conditions (Table 1). We first tested the reaction with AuCl3 in the presence and absence of AgOTf. The catalysts were not active enough to complete the reaction within an acceptable reaction condition (80 C, 18 h) (entries 1 and 2). Hg(OTf)2-(TMU)3 complex, 8