Financial support was provided by a Grant-in-Aid for Young Scientists (S) and Scientific Research (S) from JSPS. Y.S. and H.U. thank the JSPS for research fellowships.
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Catalytic Asymmetric Total Synthesis of ent-Hyperforin†
Article first published online: 8 JAN 2010
DOI: 10.1002/anie.200906678
Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Shimizu, Y., Shi, S.-L., Usuda, H., Kanai, M. and Shibasaki, M. (2010), Catalytic Asymmetric Total Synthesis of ent-Hyperforin. Angew. Chem. Int. Ed., 49: 1103–1106. doi: 10.1002/anie.200906678
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Publication History
- Issue published online: 26 JAN 2010
- Article first published online: 8 JAN 2010
- Manuscript Received: 26 NOV 2009
Funded by
- JSPS
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- 5, , , , , , , Angew. Chem. 2007, 119, 5311;Angew. Chem. Int. Ed. 2007, 46, 5219.Direct Link:Direct Link:
- 6, , , , , , , , Proc. Natl. Acad. Sci. USA 2000, 97, 7500.
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- 8d, , , Angew. Chem. 2007, 119, 8996;Angew. Chem. Int. Ed. 2007, 46, 8840;Direct Link:Direct Link:
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- 9Synthetic studies of PPAPs (representative examples):
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- 10In this study, chiral ligand 6 derived from inexpensive (R)-4-hydroxyphenylglycine was used in the catalytic asymmetric Diels–Alder reaction between 7 and 8, thus resulting in the synthesis of the antipode of natural 1.
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- 12During the scale-up studies, it was found that the enantioselectivity of this catalytic Diels–Alder reaction was improved to up to 96 % ee (87 % ee in Ref. [11]) by using strict temperature control and moisture exclusion.
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- 13aSee the Supporting Information for details;
- 13bwhen the catalytic asymmetric Diels–Alder reaction was conducted on greater than 10 g scales, a decline in the ee value was observed, probably because of the slight increase in the reaction temperature during the addition of substrates.
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- 16The hydrolysis of the enol TIPS ether provided a 1:1 mixture of C1 isomers. Although further conversion was described from one isomer (14) in the text, the other isomer was also utilized for the synthesis of intermediate 10 with comparable efficiency; see the Supporting Information for details.
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