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Diastereoselective Rhodium-Catalyzed [(3+2+2)] Carbocyclization Reactions with Tethered Alkynylidenecyclopropanes: Synthesis of the Tremulane Sesquiterpene Natural Products

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Title
Diastereoselective Rhodium-Catalyzed [(3+2+2)] Carbocyclization Reactions with Tethered Alkynylidenecyclopropanes: Synthesis of the Tremulane Sesquiterpene Natural Products
Author(s)
Evans, P. Andrew; Dushnicky, Molly J.; Dasol Cho; Majhi, Jadab; Seulhui Choi; Pipaliya, Bhavin V.; Inglesby, Phillip A.; Mu-Hyun Baik
Publication Date
2021-08
Journal
ASIAN JOURNAL OF ORGANIC CHEMISTRY, v.10, no.8, pp.2174 - 2183
Publisher
WILEY-V C H VERLAG GMBH
Abstract
The development of a diastereoselective intramolecular rhodium-catalyzed [(3+2+2)] carbocyclization reactions of allyl ester-tethered alkynylidenecyclopropanes (ACPs) for the construction of the 5,7,5-tricyclic scaffold of the tremulane sesquiterpene natural products is described. This work illustrates that the stereoelectronic nature of the phosphite ligand is critical for attaining high levels of stereocontrol, which is supported by density functional theory (DFT) studies that indicate the migratory insertion step favors the formation of the cis-diastereoisomer. Consequently, several strategies were devised to access the thermodynamically more stable trans-diastereoisomer for the synthesis of the tremulanes; however, the attempts to either switch the sense of stereocontrol in the carbocyclization reaction or epimerize the C7 stereocenter of the cycloadduct provided only modest improvements. Hence, we elected to highlight the synthetic utility of this strategy with the development of concise and highly efficient syntheses of (+/-)-epi-tremulenolide A, (+/-)-epi-tremulenediol A and (+/-)-epi-ceriponol D.
URI
https://pr.ibs.re.kr/handle/8788114/10165
DOI
10.1002/ajoc.202000482
ISSN
2193-5807
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
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