Forskolin Editing via Radical Iodo- and Hydroalkylation

Pruteanu, Elena; Tappin, Nicholas D. C.; Gîrbu, Vladilena; Morarescu, Olga; Dénès, Fabrice; Kulciţki, Veaceslav; Renaud, Philippe (2021). Forskolin Editing via Radical Iodo- and Hydroalkylation. Synthesis - journal of synthetic organic chemistry, 53(7), pp. 1247-1261. Thieme 10.1055/s-0040-1706003

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The modification of highly oxygenated forskolin as well as manoyl and epi-manoyl oxide, two less functionalized model substrates sharing the same polycyclic skeleton, via intermolecular carbon-centered radical addition to the vinyl moiety has been investigated. Highly regio- and reasonably stereoselective iodine atom transfer radical addition (ATRA) reactions were developed. Unprotected forskolin afforded an unexpected cyclic ether derivative. Protection of the 1,3-diol as an acetonide led the formation of the iodine ATRA product. Interestingly, by changing the mode of initiation of the radical process, in situ protection of the forskolin 1,3-diol moiety as a cyclic boronic ester took place during the iodine ATRA process without disruption of the radical chain process. This very mild radical-mediated in situ protection of 1,3-diol is expected to be of interest for a broad range of radical and non-radical transformations. Finally, by using our recently developed tert-butyl­catechol-mediated hydroalkylation procedure, highly efficient preparation of forskolin derivatives bearing an extra ester or sulfone group was achieved.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Pruteanu, Elena; Tappin, Nicholas David Charles; Dénès, Fabrice Pierre François and Renaud, Philippe

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry

ISSN:

0039-7881

Publisher:

Thieme

Language:

English

Submitter:

Franziska Bornhauser-Rufer

Date Deposited:

24 Jun 2021 11:02

Last Modified:

24 Jun 2021 11:12

Publisher DOI:

10.1055/s-0040-1706003

BORIS DOI:

10.48350/157099

URI:

https://boris.unibe.ch/id/eprint/157099

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