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Palladium and Gold-Catalyzed transannular [4+3] cycloaddition reactions: Application to the ABCD carbon framework of Cortistatin A. A short synthesis of S-(+)-Siphonodiol. New chiral Au(I) N-heterocyclic carbene complexes and their use in intramolecular c

Craft, Derek T.
http://rave.ohiolink.edu/etdc/view?acc_num=miami1272036117

Abstract Details

2010, Doctor of Philosophy, Miami University, Chemistry and Biochemistry.
Unit I, Using allene RCM reactions, 12, 14 and 16 membered furan/allene macrocycles were synthesized. Selective epoxidation reactions and Platinum catalysis were unable to initiate a successful transannular [4+3] cycloaddition reaction from the 14 member macrocycle. However, a palladium catalyst system was then tested which produced the first reported example of a transannular [4+3] cycloaddition reaction in 37% yield. Gold catalysis showed a slight improvement on the product yield but competing rearrangement and [4+2] reactions were problematic. After changing the 3C component from an allene to a propargyl acetate, the reaction was optimized from 13 and 14 membered macrocycles using gold catalysis to generate [4+3] cycloadducts in high yield. The transannular [4+3] cycloaddition methodology was then applied to synthesizing the ABCD ring structure of Cortistatin A. Unit II, A short synthesis of S-(+)-Siphonodiol was completed utilizing a strategy which took advantage of the hidden symmetry of the molecule. Key steps in the synthesis were copper mediated alkyne coupling reactions. Unit III, Two new chiral N-Heterocyclic Carbene complexes were synthesized and the structures were confirmed using x-ray analysis. These complexes were found to be useful as catalysts and showed similar reactivity to Au(I)IPr in intramolecular cyclopropanation reactions from propargyl acetate/alkene substrates.
Benjamin Gung, PhD (Advisor)
Richard Taylor, PhD (Committee Chair)
James Hershberger, PhD (Committee Member)
David Tierney, PhD (Committee Member)
Gary Janssen, PhD (Committee Member)
208 p.
Chemistry
transannular; cycloaddition; Cortistatin A; Gold

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Citations

  • Craft, D. T. (2010). Palladium and Gold-Catalyzed transannular [4+3] cycloaddition reactions: Application to the ABCD carbon framework of Cortistatin A. A short synthesis of S-(+)-Siphonodiol. New chiral Au(I) N-heterocyclic carbene complexes and their use in intramolecular c [Doctoral dissertation, Miami University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=miami1272036117

    APA Style (7th edition)

  • Craft, Derek. Palladium and Gold-Catalyzed transannular [4+3] cycloaddition reactions: Application to the ABCD carbon framework of Cortistatin A. A short synthesis of S-(+)-Siphonodiol. New chiral Au(I) N-heterocyclic carbene complexes and their use in intramolecular c. 2010. Miami University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=miami1272036117.

    MLA Style (8th edition)

  • Craft, Derek. "Palladium and Gold-Catalyzed transannular [4+3] cycloaddition reactions: Application to the ABCD carbon framework of Cortistatin A. A short synthesis of S-(+)-Siphonodiol. New chiral Au(I) N-heterocyclic carbene complexes and their use in intramolecular c." Doctoral dissertation, Miami University, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=miami1272036117

    Chicago Manual of Style (17th edition)

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© 2010, all rights reserved.
This open access ETD is published by Miami University and OhioLINK.