Nicholas reactions of 2,5-heptadiyne diether and ether/acetate tetracobalt complexes and synthesis of cyclophanediynes.
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In this study, two new tetracobalt dodecacarbonyl diyne complexes ( 123 and 124) suitable for the Nicholas reaction were prepared. The Nicholas reaction of the cobalt-complexed 1-acetoxy-7-benzyloxy-2,5-heptadiyne (123) and 1-methoxy-7-benzyloxy-2,5-heptadiyne (124) with several nucleophiles (125-129) afforded the corresponding alkylated products (130--135) with high regioselectivities. By a stepwise reaction, additionally, two different substitutents (allyl and trimethoxyphenyl) were introduced on the two ends of the hepta-2,5-diyne unit in a high yield. During the process of study, a new class of cyclophanediynes ( 141, 144, 148, 152, 155 and 158) was synthesized by the Nicholas reaction of 124 with electron-rich aromatics ( 138, 143, 147, 149, 154 and 156). X-Ray crystallography of the decomplexation product (124) of 141 revealed the real structure of this class of products; by which their 1H NMR properties could be explained. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1999 .G86. Source: Masters Abstracts International, Volume: 40-03, page: 0710. Adviser: Jim Green. Thesis (M.Sc.)--University of Windsor (Canada), 1999.
Guo, Ruichao., "Nicholas reactions of 2,5-heptadiyne diether and ether/acetate tetracobalt complexes and synthesis of cyclophanediynes." (1999). Electronic Theses and Dissertations. 2853.