Total synthesis of (+)-roxaticin via C-C bond forming transfer hydrogenation: a departure from stoichiometric chiral reagents, auxiliaries, and premetalated nucleophiles in polyketide construction.
A total synthesis of the oxo-polyene macrolide (+)-roxaticin is achieved in 20 steps from 1,3-propanediol. In this approach, 9 of 10 C-C bonds formed in the longest linear sequence are made via metal catalysis, including 7 C-C bonds formed by iridium catalyzed alcohol C-C coupling. Notably, the present synthesis, which represents the most concise preparation of any oxo-polyene macrolide reported to date, is achieved in the absence of chiral reagents and chiral auxiliaries with minimal use of premetalated C-nucleophiles.
University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712, USA.
Soo Bong
SB
Han
Abbas
A
Hassan
In Su
IS
Kim
Michael J
MJ
Krische
D002384:Catalysis; D006865:Hydrogenation; D007495:Iridium / Q000737:chemistry; D018942:Macrolides / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
D018942:Macrolides; C480363:roxaticin; D007495:Iridium