2011 Theses Doctoral

Studies towards Selective Synthesis of Resveratrol-based Oligomeric Natural Products

Lin, Yunqing

𝘊𝘩𝘢𝘱𝘵𝘦𝘳 1. 𝘙𝘦𝘤𝘦𝘯𝘵 𝘴𝘺𝘯𝘵𝘩𝘦𝘵𝘪𝘤 𝘢𝘱𝘱𝘳𝘰𝘢𝘤𝘩𝘦𝘴 𝘵𝘰𝘸𝘢𝘳𝘥𝘴 𝘵𝘩𝘦 𝘳𝘦𝘴𝘷𝘦𝘳𝘢𝘵𝘳𝘰𝘭 𝘧𝘢𝘮𝘪𝘭𝘺 𝘰𝘧 𝘰𝘭𝘪𝘨𝘰𝘮𝘦𝘳𝘪𝘤 𝘯𝘢𝘵𝘶𝘳𝘢𝘭 𝘱𝘳𝘰𝘥𝘶𝘤𝘵𝘴. This chapter outlines some of the past and present efforts in the field of resveratrol-based oligomeric natural product synthesis. Both biosynthetic approaches and stepwise synthetic approaches are discussed to present the current level of understanding regarding the controlled synthesis of these molecules in order to place the studies described in chapter 2 and 3 in better context.

𝘊𝘩𝘢𝘱𝘵𝘦𝘳 2. 𝘋𝘦𝘷𝘦𝘭𝘰𝘱𝘮𝘦𝘯𝘵 𝘰𝘧 𝘢 𝘨𝘦𝘯𝘦𝘳𝘢𝘭 𝘴𝘺𝘯𝘵𝘩𝘦𝘵𝘪𝘤 𝘮𝘦𝘵𝘩𝘰𝘥 𝘵𝘰𝘸𝘢𝘳𝘥𝘴 𝘥𝘪𝘧𝘧𝘦𝘳𝘦𝘯𝘵 𝘥𝘪𝘮𝘦𝘳𝘪𝘤 𝘴𝘵𝘳𝘶𝘤𝘵𝘶𝘳𝘦𝘴 𝘰𝘧 𝘵𝘩𝘦 𝘳𝘦𝘴𝘷𝘦𝘳𝘢𝘵𝘳𝘰𝘭 𝘧𝘢𝘮𝘪𝘭𝘺. We have developed a general approach to achieve selective synthesis of the major dimeric architectures within the resveratrol family with the use of a unique key common intermediate possessing three aryl rings. Syntheses of three subclasses of resveratrol dimeric structures are reported.

𝘊𝘩𝘢𝘱𝘵𝘦𝘳 3. 𝘚𝘺𝘯𝘵𝘩𝘦𝘵𝘪𝘤 𝘦𝘧𝘧𝘰𝘳𝘵𝘴 𝘵𝘰𝘸𝘢𝘳𝘥𝘴 𝘥𝘪𝘩𝘺𝘥𝘳𝘰𝘣𝘦𝘯𝘻𝘰𝘧𝘶𝘳𝘢𝘯-𝘤𝘰𝘯𝘵𝘢𝘪𝘯𝘪𝘯𝘨 𝘩𝘪𝘨𝘩𝘦𝘳 𝘰𝘳𝘥𝘦𝘳 𝘳𝘦𝘴𝘷𝘦𝘳𝘢𝘵𝘳𝘰𝘭 𝘰𝘭𝘪𝘨𝘰𝘮𝘦𝘳𝘴. Finally, this chapter describes our current studies towards more complex members of the resveratrol family. A concise approach for dihydrobenzofuran ring installation on the sevenmembered carbon framework of resveratrol-based oligomers is reported. The formation of 7,5- fused ring natural product cores 𝘷𝘪𝘢 Friedel-Crafts cyclizations provides controlled access to some of the highly complex architectures within the resveratrol family.