Development of Oxidative Coupling Transformations and Their Application in the Enantioselective Total Synthesis of Bismurrayaquinone A.

摘要

Oxidative coupling reactions are powerful tools for the synthesis of organic molecules. The use of oxidative coupling transforms allows one to approach synthesis in a different way: allowing for the retrosynthetic disconnection of 1,4-dicarbonyls into relatively simple coupling partners that have similar complexity but traditionally dissonant reactivity.;Initial studies showed that silyl bis-enol ethers could be used to template the diastereoselective formation of 1,4-diketones in good yields and excellent diastereoselectivity. This silicon tether methodology was then extended to allylsilanes where it was shown that under similar reaction conditions oxidative allylation of ketones could be achieved.;The efficient synthesis of 1,4-diketones sparked our interest into investigating them as potential biaryl surrogates. Utilizing an sp3 to sp 2 chirality exchange approach, we were able to synthesize a wide variety of axially chiral biaryl compounds. One of those biaryls was then used in the first enantioselective total synthesis of bismurrayaquinone A.;Finally, utilizing another oxidative coupling approach, a scalable synthesis of metacycloprodigiosin is reported. The biological activity of metacycloprodigiosin, prodigiosin R1, streptorubin B, butylcycloheptyl prodigiosin, and undecylprodigiosin was also investigated.