Regiochemical studies for nucleophilic addition on allylic acetate cycloheptyne cobalt complexes and the progression towards the synthesis of 7,5-bicyclic ring systems containing the cobalt complex.
Date of Award
Chemistry and Biochemistry
CC BY-NC-ND 4.0
There are several naturally occurring compounds that have fused 7,5-bicyclic ring systems. This thesis will focus on approaches to synthesizing 7,5-bicyclic systems containing a dicobalt hexacarbonyl complex. In this context, the allylic acetate cycloheptenyne complex (66) was reacted with various carbon- and hetero-based nucleophiles to determine the regiochemistry of the substitution. The gamma to alpha ratio for carbon-based nucleophiles were approximately 4:1, while hetero-based nucleophiles were 100% gamma. Once the ratios were established, several of these product compounds, which contained an electrophilic site, were investigated for further reaction to form the additional ring (Scheme 28). Formation of a 7,5-bicyclic ketone 131, alcohol 132 and diol 133 were observed when compound 129 was mixed with boron trifluoride (Scheme 42).Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis2004 .D56. Source: Masters Abstracts International, Volume: 43-01, page: 0218. Thesis (M.Sc.)--University of Windsor (Canada), 2004.
DiMartino, Joseph., "Regiochemical studies for nucleophilic addition on allylic acetate cycloheptyne cobalt complexes and the progression towards the synthesis of 7,5-bicyclic ring systems containing the cobalt complex." (2004). Electronic Theses and Dissertations. 3295.