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A stereoselective total synthesis of O,N‐dimethylhamatine, an analogue of an axially chiral naphthylisoquinoline natural biaryl product from tropical Ancistrocladus lianas, is reported. The route features a late‐stage atropo‐diastereoselective biaryl bond formation. Generation of this especially challenging, sterically hindered tetra‐ortho‐substituted array was achieved by using Nolan's (IPr*NHC)PdCinCl...
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