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Synfacts 2020; 16(07): 0763
DOI: 10.1055/s-0040-1707015
Synthesis of Natural Products and Potential Drugs
© Georg Thieme Verlag Stuttgart · New York

Synthesis of (±)-Daphnilactone A

Contributor(s):
Erick M. Carreira
,
David M. Fischer
Ruggeri RB, McClure KF, Heathcock CH. * University of California, Berkeley, USA
Daphniphyllum Alkaloids. Part 5. Total Synthesis of (±)-Daphnilactone A: A Novel Fragmentation Reaction.

J. Am. Chem. Soc. 1989;
111: 1530-1531
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Publication History

Publication Date:
17 June 2020 (online)

 
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Key words

(±)-daphnilactone A - aza-Cope rearrangement - Reformatsky reaction - daphniphyllum alkaloids - Swern oxidation - Jones oxidation - hetero-Diels–Alder reaction - Prins cyclization

Significance

In 1989, Heathcock and co-workers reported the first total synthesis of (±)-daphni­lactone A through a key fragmentation reaction. The natural product is unique among the daphniphyllium alkaloids, because it features 23 carbons, thereof one not derived from squalene.


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Comment

Reformatsky reaction and alkylation of bromoester B yielded C. Hetero-Diels–Alder reaction followed by Prins cyclization rapidly forged ­aminoether E. The key fragmentation reaction after reduction of E gave rise to single product H. This reaction could proceed either via intermediate F followed by aza-Cope rearrangement to less strained iminium G or by direct C–C cleavage to G.


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