Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published January 2, 2015 | Published + Supplemental Material
Journal Article Open

Evolution of a Unified, Stereodivergent Approach to the Synthesis of Communesin F and Perophoramidine


Expedient synthetic approaches to the highly functionalized polycyclic alkaloids communesin F and perophoramidine are described using a unified approach featuring a key decarboxylative allylic alkylation to access a crucial and highly congested 3,3-disubstituted oxindole. Described are two distinct, stereoselective alkylations that produce structures in divergent diastereomeric series possessing the critical vicinal all-carbon quaternary centers needed for each synthesis. Synthetic studies toward these challenging core structures have revealed a number of unanticipated modes of reactivity inherent to these complex alkaloid scaffolds. Additionally, several novel and interesting intermediates en route to the target natural products, such as an intriguing propellane hexacyclic oxindole encountered in the communesin F sequence, are disclosed. Indeed, such unanticipated structures may prove to be convenient strategic intermediates in future syntheses.

Additional Information

© 2014 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: November 5, 2014. Publication Date (Web): November 17, 2014. The authors wish to thank NIH-NIGMS (R01GM080269), Amgen, the Gordon and Betty Moore Foundation, and Caltech for financial support. S.-J.H. thanks Fulbright (Foreign Student Program, No. 15111120) and the Ilju Foundation of Education & Culture (Predoctoral Research Fellowship) for financial support. F.V. thanks the German Academic Exchange Service (DAAD) for a postdoctoral fellowship. J.A.M. is grateful for a fellowship by Bristol-Myers Squibb and Amgen. S.K. thanks California TRDRP for financial support (postdoctoral fellowship 14FT-0002). M.G. is grateful to the Swiss National Science Foundation for financial support (postdoctoral fellowship). Dr. David VanderVelde (Caltech) is gratefully acknowledged for assistance with the characterization of compounds by NMR spectroscopy. Lawrence Henling (Caltech) is acknowledged for X-ray crystallographic structural determination. The authors are thankful to Dr. Ryan Zeidan, Dr. Sandy Ma, and Mr. Chung Whan Lee for experimental assistance.

Attached Files

Published - jo502534g.pdf

Supplemental Material - jo502534g_si_001.pdf

Supplemental Material - jo502534g_si_002.cif

Supplemental Material - jo502534g_si_003.cif

Supplemental Material - jo502534g_si_004.cif

Supplemental Material - jo502534g_si_005.cif

Supplemental Material - jo502534g_si_006.cif

Supplemental Material - jo502534g_si_007.cif

Supplemental Material - jo502534g_si_008.cif

Supplemental Material - jo502534g_si_009.cif

Supplemental Material - jo502534g_si_010.cif

Supplemental Material - jo502534g_si_011.cif

Supplemental Material - jo502534g_si_012.cif

Supplemental Material - jo502534g_si_013.cif

Supplemental Material - jo502534g_si_014.cif


Files (37.1 MB)
Name Size Download all
19.7 kB Download
14.4 kB Download
3.5 MB Download
3.3 MB Download
19.3 kB Download
1.5 MB Download
3.8 MB Preview Download
3.2 MB Download
13.3 MB Preview Download
4.1 kB Download
6.6 MB Download
25.3 kB Download
20.3 kB Download
16.8 kB Download
1.9 MB Download

Additional details

August 20, 2023
August 20, 2023