Indole diterpenoid synthetic studies: The total synthesis of (+)-nodulisporic acid F and studies toward the total synthesis of (-)-nodulisporic acid D.

摘要

Chapter one of this dissertation provides a general introduction to the indole diterpenoid class of natural products, with an emphasis on the recently discovered nodulisporic acids. Chapter two describes the stereocontrolled total synthesis of (+)-nodulisporic acid F. Highlights of the modular synthetic strategy include an efficient anionic coupling via the Smith 2-substituted indole synthesis, an optimized C-ring annulation protocol, and a late-stage installation of the alpha,beta-unsaturated carboxylic acid sidechain via the B-alkyl Suzuki-Miyaura cross-coupling reaction.*; Chapter three details our overall strategy for the convergent, asymmetric total synthesis of (-)-nodulisporic acid D, a representative member of a recently nodulisporane class of architecturally complex indole alkaloids. In addition, we describe an expedient, stereocontrolled preparation of tricyclic western hemisphere subtarget (-)-104. Successful union of (-)- 104 with eastern hemisphere subtarget (-)-125 via our 2-substituted indole synthesis has enabled construction of the heptacyclic core of (-)-nodulisporic acid D.*; *Please refer to dissertation for diagrams.