Total Syntheses of Heimiol A, Hopeahainol D, and Constrained Analogues†
Corresponding Author
Prof. Dr. Scott A. Snyder
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027 (USA) http://www.columbia.edu/cu/chemistry/groups/snyder/
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027 (USA) http://www.columbia.edu/cu/chemistry/groups/snyder/Search for more papers by this authorNathan E. Wright
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027 (USA) http://www.columbia.edu/cu/chemistry/groups/snyder/
Search for more papers by this authorJason J. Pflueger
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027 (USA) http://www.columbia.edu/cu/chemistry/groups/snyder/
Search for more papers by this authorSteven P. Breazzano
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027 (USA) http://www.columbia.edu/cu/chemistry/groups/snyder/
Search for more papers by this authorCorresponding Author
Prof. Dr. Scott A. Snyder
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027 (USA) http://www.columbia.edu/cu/chemistry/groups/snyder/
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027 (USA) http://www.columbia.edu/cu/chemistry/groups/snyder/Search for more papers by this authorNathan E. Wright
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027 (USA) http://www.columbia.edu/cu/chemistry/groups/snyder/
Search for more papers by this authorJason J. Pflueger
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027 (USA) http://www.columbia.edu/cu/chemistry/groups/snyder/
Search for more papers by this authorSteven P. Breazzano
Department of Chemistry, Columbia University, Havemeyer Hall, 3000 Broadway, New York, NY 10027 (USA) http://www.columbia.edu/cu/chemistry/groups/snyder/
Search for more papers by this authorWe thank the NSF (CHE-0619638) for an X-ray diffractometer and Prof. Gerard Parkin, Wesley Sattler, and Aaron Sattler for performing all of the crystallographic analyses. We also thank Adel ElSohly for performing the calculations. Financial support was provided by Columbia University, the National Institutes of Health (R01GM84994), Bristol-Myers Squibb, Eli Lilly, the NSF (Predoctoral Fellowships to N.E.W. and S.P.B.), the ACS Division of Organic Chemistry (summer fellowship to J.J.P.), and the Research Corporation for Science Advancement (Cottrell Scholar Award to S.A.S.).
Graphical Abstract
Ein Reagens namens IDSI, [(Et2SI)2Cl⋅ SbCl6], löst eine sorgsam entworfene Reaktionskaskade aus, die den zentralen [3.2.2]Bicyclus beider Zielverbindungen, 1 und 2, in einer einzigen stereokontrollierten Operation liefert. Auf dem weiteren Weg zu den Naturstoffen wurden Spannungsenergien genutzt.
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References
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- 14Intriguingly, use of either of these reagents separately did not afford the desired product.
- 15It is worth noting that if 17 was first added to aldehyde 14, no attempt at subsequent haloetherification to reach 20 directly succeeded in any observable yield (although at best only 50 % of material could be advanced to the desired product due to the extra stereogenic center).
- 16Earlier protection of the phenols as benzyl ethers prevented the smooth preparation of alcohol 13 because of issues of additional strain imparted by these groups in forging critical CC bonds.
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- 19Conditions attempted included exposure to acid and heat, as well as the trityl cation to try and establish a dynamic equilibrium.
- 20For recent examples with other unique polyphenolic natural products, see:
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10.1002/ange.201000044 Google ScholarAngew. Chem. Int. Ed. 2011, 50, 586–621. For recent work to prepare oligomeric polyphenols beyond the dimer level, see:
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