- Me2AlSEt-promoted domino dieckmann cyclization enables the total synthesis of polycyclic polyprenylated acylphloroglucinols
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A bioinspired, Me2AlSEt-promoted domino Dieckmann cyclization via an 8-membered ring intermediate to construct bicyclo[3.3.1]nonanes was developed, and the divergent syntheses of nine complex polycyclic polyprenylated acylphloroglucinols were a
- Wang, Liping,Sun, Lian,Wang, Xueying,Wu, Rong,Zhou, Hua,Zheng, Changwu,Xu, Hongxi
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p. 8075 - 8079
(2019/10/14)
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- The enantioselective total synthesis of (+)-clusianone
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(+)-Clusianone, an exo-type B PPAP with reported anti-HIV and chemoprotective activities, was synthesized in eleven steps with 97% ee starting from acetylacetone. An enantioselective decarboxylative Tsuji-Trost-allylation and a Ru-catalyzed ring-closing metathesis-decarboxylative allylation were used to control both diastereo- and enantioselectivity.
- Horeischi, Fiene,Guttroff, Claudia,Plietker, Bernd
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p. 2259 - 2261
(2015/02/05)
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- Asymmetric, stereodivergent synthesis of (-)-clusianone utilizing a biomimetic cationic cyclization
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We report a stereodivergent, asymmetric total synthesis of (-)-clusianone in six steps from commercial materials. We implement a challenging cationic cyclization forging a bond between two sterically encumbered quaternary carbon atoms. Mechanistic studies point to the unique ability of formic acid to mediate the cyclization forming the clusianone framework. Aim for selectivity: (-)-Clusianone was produced by a stereodivergent asymmetric total synthesis in six steps from commercial materials. The synthesis utilizes a challenging formic acid-mediated cationic cyclization forging a bond between two sterically encumbered quaternary carbon atoms.
- Boyce, Jonathan H.,Porco, John A.
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p. 7832 - 7837
(2014/08/05)
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- The total synthesis of hyperpapuanone, hyperibone L, epi-clusianone and oblongifolin A
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Polyprenylated polycyclic acylphloroglucines (PPAPs) are a family of natural products that possess a wide range of different important biological activities because of the relative position and configuration of four substituents that decorate one common c
- Biber, Nicole,Moews, Katrin,Plietker, Bernd
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p. 938 - 942
(2012/03/08)
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- Development of a strategy for the asymmetric synthesis of polycyclic polyprenylated acylphloroglucinols via N-amino cyclic carbamate hydrazones: Application to the total synthesis of (+)-clusianone
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A broadly applicable asymmetric synthetic strategy utilizing N-amino cyclic carbamate alkylation that provides access to the various stereochemical permutations of a common structural motif found in many polycyclic polyprenylated acylphloroglucinols is de
- Garnsey, Michelle R.,Lim, Daniel,Yost, Julianne M.,Coltart, Don M.
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supporting information; experimental part
p. 5234 - 5237
(2011/02/23)
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- Synthesis of polyprenylated acylphloroglucinols using bridgehead lithiation: The total synthesis of racemic clusianone and a formal synthesis of racemic garsubellin A
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(Chemical Equation Presented) The synthesis of polyprenylated phloroglucinol natural products, including clusianone, nemorosone, and garsubellin A, was pursued by a strategy involving construction of a core bicyclo[3.3.1]nonanetrione structure and subsequent elaboration via organolithium intermediates. Appropriate bridged core structures were obtained through the cyclization of a suitably substituted cyclohexanone enol ether or enol silane with malonyl dichloride. Additional substituents were then introduced by means of regioselective lithiation reactions, including the generation of bridgehead enolates, thus enabling the total synthesis of clusianone and also of an advanced intermediate toward nemorosone. In the case of garsubellin A, an additional THF-like ring was elaborated by a biomimetic 5-exo-tet cyclization of an enol ether (or enol) with a side-chain epoxide. This enabled a formal synthesis of racemic garsubellin A by accessing one of the late intermediates in the Danishefsky synthesis.
- Ahmad, Nadia M.,Rodeschini, Vincent,Simpkins, Nigel S.,Ward, Simon E.,Blake, Alexander J.
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p. 4803 - 4815
(2008/02/05)
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- Differentiation of nonconventional "carbanions" - The total synthesis of nemorosone and clusianone
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(Chemical Equation Presented) An unconventional approach: The total syntheses of nemorosone (1) and clusianone (2) have been achieved in a direct fashion through the generation and exploitation of nonconventional anions arising from a common intermediate
- Tsukano, Chihiro,Siegel, Dionicio R.,Danishefsky, Samuel J.
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p. 8840 - 8844
(2008/10/09)
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