Synthetic Studies Directed toward the Eremantholides. 2. A Novel Application of the Ramberg-Bäcklund Rearrangement to a Highly Stereoselective Synthesis of (+)-Eremantholide A

Journal of the American Chemical Society

Volumn 113, Issue 25, 1991, Pages 9682-9684

  Boeckman, Robert K ^a   Yoon, Suk Kyoon ^a   Heckendorn, Debra K ^a  

^a UNIVERSITY OF ROCHESTER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 84889398397     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00025a049     Document Type: Letter

References (46)

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27. Decoupling experiments confirmed that HC(C8) is trans diaxial to Ha (C9) and Hd (C7), as is required by the large coupling constants (Jac = Jde = 12 Hz) between Ha and Hc, and Hd and He (C11); thus, the OH group at C8 in 21 is α (as depicted for 1).
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43. Less hindered bases afforded 33, which is unstable to extended exposure to strong base, along with ∼20% of 31.
44. Naturally derived 33, prepared from natural (+)−1,33 was identical to synthetic 33 by the usual spectroscopic criteria.
45. Synthetic (+)−1 was identical (IR, NMR, MS, [α]D, and TLC in several solvents) to authentic natural (+)−1.33
46. We thank Professor P. W. LeQuesne (Northeastern University) for a sample of natural (+)-eremantholide A (1).