Dissertation/Thesis Abstract

Progress toward the synthesis of an osmium-diimine electron tunneling wire and synthesis of racemic fusarochromanone-(±)-FC-101
by Dong, Z. Eric, Ph.D., University of South Carolina, 2008, 261; 3336687
Abstract (Summary)

Chapter 1. The preparation of the dmbpy-C6F4-C6F4-Im ligand (6) had been modified by changing the synthetic order. Consequently, the isolated yield was increased significantly from 11% to 33% over two steps. However, the final step to complex this ligand (6) with (bpy)2OsCl2 (15b) to synthesize the target Os-diimine electron tunneling wire (Im-C6F4-C6F4-dmbpy)Os(bpy)2Cl2 (8b) proved difficult. Attempts to react 6 with 15b directly, or via anion exchange of 15b with CF3SO3-, PF6-, etc., were unsuccessful.

Chapter 2. Racemic FC-101 (±-80) as well as the model compound (150) have been synthesized via osmium-catalyzed dihydroxylation. Detailed investigation suggests that the poor selectivity during the dihydroxylation step, together with partial racemization during azide displacement, contributed to the formation of a racemic product. Nonetheless, this study paves the road to the eventual synthesis of both enantiomeric pure FC-101 and its (S)-enantiomer. 2,2-Dimethyl-6-iodo-5-nitrochroman-4-ol (96a), the key intermediate towards FC-101, was prepared from p-anisidine in 7 steps. Heck Reaction of protected vinyl glycine (90b and 90c) with both iodochromanol and iodonitrobenzene, and the chemistry of the corresponding products, together with Suzuki Coupling of protected vinyl glycine (90b and 90c) with iodonitrobenzene, and the chemistry of the corresponding products, have been intensively investigated, even though attempt to prepare model compound (150) via Suzuki-Miyama or Heck reaction was unsuccessful.

Indexing (document details)
Advisor: Dawson, John H., Wuthier, Roy E.
Commitee: Chapman, James M., Wiskur, Sheryl L.
School: University of South Carolina
Department: Chemistry
School Location: United States -- South Carolina
Source: DAI-B 69/11, Dissertation Abstracts International
Source Type: DISSERTATION
Subjects: Organic chemistry
Keywords: 2-dimethyl-6-iodo-5-nitrochroman-4-ol, Electron tunneling, FC-101, Fusarochromanone, Osmium-diimine electron tunneling wire, Sharpless dihydroxylation
Publication Number: 3336687
ISBN: 9780549904106
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