Gold-catalyzed Rearrangement Reaction Of Propargylic Aziridine And Synthetic Study Of Daphniphyliunl Alkaloids Tenuipesine A

The thesis aims at the studies of Au(I)-catalyzed tandemn rearrangement reaction of propargylic aziridine and the total synthesis of two kinds of natural products containing the contiguous stereogenic quaternary carbons:Longeracinphyllins A and Tenuipesine A. It mainly consists of the following two parts:Part Ⅰ:A rearrangement reaction of propargylic aziridine, catalyzed by PPh3AuCl/AgOTf, forming trisubstituted and cycloalkene-fused pyrroles is described which involves an unusual tandem cyclization/ring-opening/Wagner-Meerwein process.Part Ⅱ:Synthetic studies on two natural products containing contiguous stereogenic quaternary carbons.1. In the exploration to the synthesis of basic skeleton of Longeracinphyllins A, we successfully constructed the spiro-quaternary carbon nucleus based on the Brosted acid induced semipinacol rearrangement of allylic alcohol. Although we did not acomplish the total synthesis of target molecule, all these information obtained would be voluable to the continued investigations.2. During the process of synthesis of Tenuipesine A, using the (O-alkylation/Claisen rearrangement reaction sequence of β-ketoester and geraniol, we smoothly constructed the two contiguous stereogenic quaternary carbons. And then we obtained the tricyclic skeleton of Tenuipesine A utilizing ring-closing metathesis(RCM) and Simmons-Smith cyclopropanation.