The total synthesis of a natural cardenolide: (+)-digitoxigenin

Journal of the American Chemical Society

Volumn 118, Issue 43, 1996, Pages 10660-10661

  Stork, Gilbert ^a   West, Fred ^a,b   Lee, Hee Yoon ^a,c   Isaacs, Richard C A ^a,d   Manabe, Shino ^a,e  

^a Columbia University ^*  (United States)

^b UNIVERSITY OF UTAH   (United States)

^c Korea Advanced Institute of Science and Technology (KAIST)   (South Korea)

^d MERCK RESEARCH LABORATORIES   (United States)

^e TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CARDENOLIDE; DIGITOXIGENIN;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; ENANTIOMER; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS;

EID: 0029844604     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja962163m     Document Type: Article

References (51)

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42. 3 center.
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44. This was accompanied by ∼ 16% of the product of reduction without cyclization and ∼ 19% of the product from rearrangement of the intermediate cyclized homoallylic radical, for example, see: (a) Stork, G.; Mook, R., Jr. Tetrahedron Lett. 1986, 27, 4529. (b) Beckwith, A. L. J.; O'Shea, D. M. Tetrahedron Lett. 1986, 27, 4525. The vinyl radical cyclization step to 16 was improved (65%) when it was carried out via the 2-iodobutene derivable from 15, but the overall yield was unaffected.
45. Concerted rearragement of the epoxide should have led to the desirable β aldehyde, itself stable to the rearrangement conditions. Formation, however, of the α epimer implies that rearragement probably proceeds to the aldehyde enol in this case.
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