Enantioselective Total Syntheses of (+)-Hippolachnin A, (+)-Gracilioether A, (-)-Gracilioether E and (-)-Gracilioether F
Li, Q., Zhao, K., Peuronen, A., Rissanen, K., Enders, D., & Tang, Y. (2018). Enantioselective Total Syntheses of (+)-Hippolachnin A, (+)-Gracilioether A, (-)-Gracilioether E and (-)-Gracilioether F. Journal of the American Chemical Society, 140 (5), 1937-1944. doi:10.1021/jacs.7b12903
Published inJournal of the American Chemical Society
© 2018 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by American Chemical Society. Published in this repository with the kind permission of the publisher.
The Plakortin polyketides represent a structurally and biologically fascinating class of marine natural products. Herein, we report a unified strategy that enables the divergent syntheses of various Plakortin polyketides with high step-economy and overall efficiency. As proof-of-concept cases, the enantioselective total syntheses of (+)-hippolachnin A, (+)-gracilioether A, (−)-gracilioether E, and (−)-gracilioether F have been accomplished based on a series of bio-inspired, rationally designed, or serendipitously discovered transformations, which include (1) an organocatalytic asymmetric 1,4-conjugate addition to assemble the common chiral γ-butenolide intermediate enroute to all of the aforementioned targets, (2) a challenging biomimetic [2+2] photocycloaddition to forge the oxacyclobutapentalene core of (+)-hippolachnin A, (3) a [2+2] photocycloaddition followed by one-pot oxidative cleavage of methyl ether/Baeyer–Villiger rearrangement to access (−)-gracilioether F, and (4) an unprecedented hydrogen-atom-transfer-triggered oxygenation of vinylcyclobutane to afford (+)-gracilioether A and (−)-gracilioether E in one pot. ...