Synthesis of the C7−C15 trans Decalin Portion of the Natural Antibiotic Tetrodecamycin

Abstract

[reaction: see text] The tandem oxy-Cope/ene/Claisen rearrangement has been developed in our laboratory as a powerful method for rapid construction of complex Decalin cores. Herein, we describe the use of this method to generate the Decalin core of the natural antibiotic tetrodecamycin (1) bearing six contiguous stereocenters.

Transition metals in organic synthesis: Highlights for the year 2005

“…Palladium catalyzed an alkene isomerization to the more substituted alkene in a synthesis of (−)-physovenine and (−)-3a-hydroxyfuroindoline [601]. Rhodium catalyzed alkene isomerizations to the more substituted alkene was used in synthesis of the C7-C15 decalin system of tetrodomycin [1473] and pandamarilactonine A [1474]. Rhodium catalyzed the isomerization of propargylic sulfinic esters to allenyl sulfones [1024].…”

Microwave-Assisted Claisen and Aza-Claisen Rearrangements

“…Synthesis of C7-C15 trans Decalin units 66a and 66b of the natural antibiotic Tetrodecamycin 67 has been accom-plished using tandem oxy-Cope/ene/CR in 16 and 18 steps, respectively [96] (Scheme (17)). The mechanism of the process is similar to the cascade depicted on Scheme (6), although in the case of alcohol 64 the diastereoselectivity of the process was diminished by the planarization of the ring imposed by unsaturated bond, which leads to the formation of the side product aldehyde 65a.…”

Total syntheses of bioactive natural products from carbohydrates

“…Moreover, the quaternary carbons are located at C 7 and C 13 [89]. The imposing structure and optical medicinal importance of this molecule have attracted a great deal of attention from the other researchers since the disclosure of the structure [90][91][92][93][94][95], although the total synthesis had not been reported until our synthesis [96].…”