Desymmetrization of Metalated Cyclohexadienes and Application to the Synthesis of Nephrosteranic Acid

Angewandte Chemie - International Edition

Volumn 43, Issue 3, 2004, Pages 313-315

  Schleth, Florian ^a   Studer, Armido ^a  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

Author keywords

Asymmetric synthesis; Natural products; Synthetic methods; TADDOLs; Titanium; Total synthesis

Indexed keywords

ALCOHOLS; ALDEHYDES; STEREOCHEMISTRY; SYNTHESIS (CHEMICAL);

ENATIOSELECTIVITY;

OLEFINS;

ALCOHOL DERIVATIVE; ALDEHYDE DERIVATIVE; ALKADIENE; NEPHROSTERANIC ACID; UNCLASSIFIED DRUG;

ALLYLATION; ARTICLE; CHEMICAL ANALYSIS; CHEMICAL BOND; CHIRALITY; COMPLEX FORMATION; DEGRADATION; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0347761351     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200352254     Document Type: Article

References (30)

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20. 4.
21. The major isomer of 4a was unambiguously assigned as the syn isomer based on X-ray structure analysis. All the other compounds were assigned in analogy. CCDC-213624 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
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26. For recent syntheses of nephrosteranic acid see: a) H. Takahata, Y. Uchida, T. Momose, J. Org. Chem. 1995, 60, 5628; P. A. Jacobi, P. Herradura, Can. J. Chem. 2001, 79, 1727; M. P. Sibi, P. Liu, J. Ji, S. Hajra, J.-x. Chen, J. Org. Chem. 2002, 67, 1738; R. B. Chhor, B. Nosse, S. Sörgel, C. Böhm, M. Seitz, O. Reiser, Chem. Eur. J. 2003, 9, 260.
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29. The regioisomeric 1,4-diene was formed as a side product and could not be separated (4o/5o 87:13). Unfortunately, we were not able to determine the enantiomer ratio of the major product 4 o. However, the same reaction with hexanal afforded the major isomer with an enantiomer ratio of 93:7, as determined by GC analysis. We assume that the reaction with dodecanal proceeds with similar selectivity.
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