| Suzuki couplings of Boc, Cbz; or phthalimide protected allylamines were accomplished using 9-BBN and alpha-iodoenones, e.g., 2-iodo-2-cyclohexen-1-one or an alpha-iodoallylic alcohols, e.g., 2-iodo-2-cyclohexen-1-ol, to produce the corresponding coupled products, e.g., 1. The removal of the protecting groups were accomplished under mild conditions. Additionally, tert-butyldiphenyisilyl protected ally] alcohol could be coupled using a similar protocol. The chemistry of alpha-iodoenones and alpha-iodoallylic alcohols was further expanded via Heck reactions with vinyl coupling partners, such as methyl acrylate, to deliver coupled products such as 2.*.;Elaborated 1,4-naphthoquinone intermediates were made enantiomerically pure through biocatalytic transformations with Pseudomonas cepacia lipase and isopropenyl acetate to afford 3 or 4. Intermediate 3 was a key intermediate in the synthesis of a small library of conduritol analogs such as 5. Acetate 4 was advanced in studies toward the ras farnesyltransferase inhibitor deoxypressumerin A.;*Please refer to dissertation for diagram. |
