Published July 8, 2014
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A unified strategy for the synthesis of (−)-maoecrystal Z, (−)-trichorabdal A, and (−)-longikaurin E
Abstract
Herein we describe in full our investigations that led to the completion of the first total syntheses of (−)-maoecrystal Z, (−)-trichorabdal A, and (−)-longikaurin E. The unified strategy employs a Ti^(III)-mediated reductive epoxide coupling to rapidly prepare a key spirolactone. Highly diastereoselective Sm^(II)-mediated reductive cyclizations and a Pd^(II)-mediated oxidative cyclization enable the construction of three architecturally distinct ent-kauranoid frameworks from this common intermediate.
Additional Information
© 2014 Elsevier Ltd. Received 19 February 2014; Received in revised form 17 March 2014; Accepted 21 March 2014; Available online 29 March 2014. We thank Mr. Larry Henling and the late Dr. Michael Day for X-ray crystallographic structure determination and Dr. David VanderVelde for assistance with NMR structure determination. We also thank Prof. Brian Stoltz, Dr. Scott Virgil, and the Caltech Center for Catalysis and Chemical Synthesis for access to analytical equipment, as well as Sigmae-Aldrich for a kind donation of chemicals. The Bruker KAPPA APEXII X-ray diffractometer was purchased through an award to the California Institute of Technology by the NSF CRIF program (CHE-0639094). S.E.R. is a fellow of the Alfred P. Sloan Foundation, a Camille Dreyfus Teacher-Scholar, and an American Cancer Society Research Scholar. Fellowship support from Bristol-Myers Squibb (_100002491) (J.T.S.Y.) and the National Science Foundation (_100000001) (Graduate Research Fellowship, V.W.M., Grant No. DGE-1144469) and financial support from the California Institute of Technology, the National Science Foundation (CAREER-1057143), Boehringer Ingelheim (_100001003), and Amgen (_100002429) are gratefully acknowledged.Attached Files
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Additional details
- Eprint ID
- 47494
- Resolver ID
- CaltechAUTHORS:20140725-092716157
- CHE-0639094
- NSF
- Alfred P. Sloan Foundation
- Camille and Henry Dreyfus Foundation
- American Cancer Society
- Bristol-Myers Squibb
- DGE-1144469
- NSF Graduate Research Fellowship
- Caltech
- CHE-1057143
- NSF
- Boehringer Ingelheim
- Amgen
- Created
-
2014-07-25Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field