Intramolecular conjugate addition reactions of amines and carbamates to 2,5-cyclohexadien-1-ones: Stereoselective synthesis of perhydroindoles

Tetrahedron

Volumn 55, Issue 29, 1999, Pages 8953-8966

  Bland, Douglas ^a   Chambournier, Gilles ^a   Dragan, Vladimir ^a   Hart, David J ^a  

^a OHIO STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; CARBAMIC ACID DERIVATIVE; INDOLE DERIVATIVE; KETONE;

CHEMICAL REACTION; CONFERENCE PAPER; PRIORITY JOURNAL; STEREOCHEMISTRY; SYNTHESIS; THERMODYNAMICS;

EID: 0033575412     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(99)00455-X     Document Type: Conference Paper

References (32)

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7. For the first total synthesis of manzamine A see: Winkler, J. D.; Axten, M. M. J. Am. Chem. Soc. 1998, 120, 6425. For a relevant review see: Matzanke, N.; Gregg, R. J.; Weinreb, S. M. Org Prep. Proc. Int. 1998, 30, 1.
8. See reference 4 for a more convergent approach to 4 that ran into complications.
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21. 3-MeOH. Cyclization of I using CsF and epimerization studies with II were not performed. The synthesis of I from a known ester [Garner, P.; Park, J. M. Organic Syntheses 1992, 70, 18] is outlined near the top of the next page. Details appear in the PhD Thesis of Gilles Chambournier, The Ohio State University, 1998.
22. -1 energy difference between 28a (lower) and 2-epi-28a.
23. 2-hybridized orbital on the carbamate nitrogen (either in the anion or an imidate tautomer). This requires a different analysis of the problem that does not lead us to an obvious explanation for our experimental observations. This problem does seem to be a good candidate for computational analysis and such studies are planned. (formula presented)
24. 2H, PhH, 77%
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28. 8a-diastereomer to 28b. These results suggest that the stereochemical course of the transformation shown Scheme 2 (38→28b) is governed by thermodynamics.
29. X-ray crystallography was performed by Dr. Judith C. Gallucci at The Ohio State University.
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31. 13C NMR were taken at 50-125 MHz in the indicated solvent and are reported as follows: chemical shift (multiplicity determined by DEPT). Chromatography was performed using either gravity or flash chromatography techniques as required. Solvents and reagents were dried and purified prior to use when deemed necessary using standard procedures. Reactions requiring an inert atmosphere were run under a blanket of argon.
32. This reagent was prepared by reaction of isobutylene with -hexyn-1-ol in hexanes in the presence of Amberlyst DV265 (Alexakis, A.; Gardette, M.; Colin, S. Tetrahedron Lett. 1988, 29, 2951).