- Magnesium dicarboxylates promote the prenylation of phenolics that is extended to the total synthesis of icaritin
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The prenylation of phenolic substrates promoted by magnesium dicarboxylates was developed. An investigation of the scope demonstrated that substrates with electron-donating group(s) gave better yields than those with electron-withdrawing group(s). Althoug
- Fu, Xuewen,Lu, Xiaoxia,Wang, Chun,Wen, Yongju,Xiong, Wei,Zhang, Guolin,Zhang, Jichao
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p. 1117 - 1124
(2022/02/16)
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- Regiospecific Prenylation of Hydroxyxanthones by a Plant Flavonoid Prenyltransferase
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C-Prenylated xanthones are pharmacologically attractive specialized metabolites that are distributed in plants and microorganisms. The prenylation of xanthones often contributes to the structural diversity and biological activities of these compounds. However, efficient regiospecific prenylation of xanthones is still challenging. In this study, the regiospecific prenylation of a number of structurally different hydroxyxanthones (3-10) by MaIDT, a plant flavonoid prenyltransferase with substrate flexibility from Morus alba, is demonstrated. Among the enzymatic products, 2-dimethylallyl-1,3,7-trihydroxyxanthone (3a) effectively attenuated glutamate-induced injury in SK-N-SH neuroblastoma cells. These results suggest a potential approach for the synthesis of bioactive prenylated xanthones by a substrate-relaxed flavonoid prenyltransferase.
- Wang, Ruishan,Chen, Ridao,Li, Jianhua,Liu, Xiao,Xie, Kebo,Chen, Dawei,Peng, Ying,Dai, Jungui
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p. 2143 - 2147
(2016/09/09)
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- Synthesis and anti-cancer activity evaluation of novel prenylated and geranylated chalcone natural products and their analogs
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Four natural chalcones bearing prenyl or geranyl groups, i.e., bavachalcone (1a), xanthoangelol (1b), isobavachalcone (1c), and isoxanthoangelol (1d) were synthesized by using a regio-selective iodination and the Suzuki coupling reaction as key steps. The first total synthesis of isoxanthoangelol (1d) was achieved in 36% overall yield. A series of diprenylated and digeranylated chalcone analogs were also synthesized by alkylation, regio-selective iodination, aldol condensation, Suzuki coupling and [1,3]-sigmatropic rearrangement. The structures of the 11 new derivatives were confirmed by 1H NMR, 13C NMR and HRMS. The anticancer activity of these new chalcone derivatives against human tumor cell line K562 were evaluated by MTT assay in vitro. SAR studies suggested that the 50-prenylation/geranylation of the chalcones significantly enhance their cytotoxic activity. Among them, Bavachalcone (1a) displayed the most potent cytotoxic activity against K562 with IC50 value of 2.7 mM. The morphology changes and annexin-V/PI staining studies suggested that those chalcone derivatives inhibited the proliferation of K562 cells by inducing apoptosis.
- Wang, Hao-Meng,Zhang, Li,Liu, Jiang,Yang, Zhao-Liang,Zhao, Hong-Ye,Yang, Yao,Shen, Di,Lu, Kui,Fan, Zhen-Chuan,Yao, Qing-Wei,Zhang, Yong-Min,Teng, Yu-Ou,Peng, Yu
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p. 439 - 448
(2015/03/05)
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- Concise synthesis of prenylated and geranylated chalcone natural products by regiospecific iodination and Suzuki coupling reactions
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Four natural chalcones bearing prenyl or geranyl groups, i.e., isobavachalcone (1), bavachalcone (2), xanthoangelol (3), and 2′,4′,4-trihydroxy-5′-geranylchalcone (isoxanthoangelol, 4) were synthesized by using a regio-selective iodination and the Suzuki coupling reaction as key steps. Among them, the first total synthesis of 2′,4′,4-trihydroxy-5′-geranylchalcone was achieved in 36% overall yield. Comparing with the reported methods based on C-alkylation or O-alkylation followed by Claisen rearrangement to introduce the side chain, this new strategy capitalizes on a precious regiochemical control during iodination. The overall yields for the synthesis of the first three chalcones were improved from 17% to 53%, 12% to 35%, and 28% to 50%, respectively.
- Wang, Haomeng,Yan, Zhihong,Lei, Yanan,Sheng, Kai,Yao, Qingwei,Lu, Kui,Yu, Peng
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supporting information
p. 897 - 899
(2014/02/14)
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- Concise synthesis of prenylated and geranylated chalcone natural products by regiospecific iodination and Suzuki coupling reactions
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Four natural chalcones bearing prenyl or geranyl groups, i.e., isobavachalcone (1), bavachalcone (2), xanthoangelol (3), and 2′,4′,4-trihydroxy-5′-geranylchalcone (isoxanthoangelol, 4) were synthesized by using a regio-selective iodination and the Suzuki coupling reaction as key steps. Among them, the first total synthesis of 2′,4′,4-trihydroxy-5′-geranylchalcone was achieved in 36% overall yield. Comparing with the reported methods based on C-alkylation or O-alkylation followed by Claisen rearrangement to introduce the side chain, this new strategy capitalizes on a precious regiochemical control during iodination. The overall yields for the synthesis of the first three chalcones were improved from 17% to 53%, 12% to 35%, and 28% to 50%, respectively.
- Wang, Haomeng,Yan, Zhihong,Lei, Yanan,Sheng, Kai,Yao, Qingwei,Lu, Kui,Yu, Peng
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supporting information
p. 897 - 899
(2015/03/03)
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- Molecular Characterization and Phylogenetic Analysis of Two Novel Regio-specific Flavonoid Prenyltransferases from Morus alba and Cudrania tricuspidata
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Prenylated flavonoids are attractive specialized metabolites with a wide range of biological activities and are distributed in several plant families. The prenylation catalyzed by prenyltransferases represents a Friedel-Crafts alkylation of the flavonoid skeleton in the biosynthesis of natural prenylated flavonoids and contributes to the structural diversity and biological activities of these compounds. To date, all identified plant flavonoid prenyltransferases (FPTs) have been identified in Leguminosae. In the present study two new FPTs, Morus alba isoliquiritigenin 3′-dimethylallyltransferase (MaIDT) and Cudrania tricuspidata isoliquiritigenin 3′-dimethylallyltransferase (CtIDT), were identified from moraceous plants M. alba and C. tricuspidata, respectively. MaIDT and CtIDT shared low levels of homology with the leguminous FPTs. MaIDT and CtIDT are predicted to be membrane-bound proteins with predicted transit peptides, seven transmembrane regions, and conserved functional domains that are similar to other homogentisate prenyltransferases. Recombinant MaIDT and CtIDT were able to regioselectively introduce dimethylallyl diphosphate into the A ring of three flavonoids with different skeleton types (chalcones, isoflavones, and flavones). Phylogenetic analysis revealed thatMaIDT and CtIDT are distantly related to their homologs in Leguminosae, which suggests that FPTs in Moraceae and Leguminosae might have evolved independently. MaIDT and CtIDT represent the first two non-Leguminosae FPTs to be identified in plants and could thus lead to the identification of additional evolutionarily varied FPTs in other non-Leguminosae plants and could elucidate the biosyntheses of prenylated flavonoids in various plants. Furthermore, MaIDT and CtIDT might be used for regiospecific prenylation of flavonoids to produce bioactive compounds for potential therapeutic applications due to their high efficiency and catalytic promiscuity.
- Wang, Ruishan,Chen, Ridao,Li, Jianhua,Liu, Xiao,Xie, Kebo,Chen, Dawei,Yin, Yunze,Tao, Xiaoyu,Xie, Dan,Zou, Jianhua,Yang, Lin,Dai, Jungui
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p. 35815 - 35825
(2015/02/19)
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- Synthesis of isobavachalcone and some organometallic derivatives
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Isobavachalcone [2′,4,4′-trihydroxy-3′-(3″-methyl- 2″-butenyl)chalcone, 1] is a prenylated chalcone that has broad biological activity, in particular against neuroblastomas, the most common cancer in infancy. It is currently commercially available at a cost of 190/mg by extraction from Psoralea corylifolia and a number of other African and Asian plants. Several synthetic routes have been explored, and the most efficient procedure involves the palladium-catalysed Stille coupling of 3-iodo-2,4-bis(methoxymethoxy)acetophenone (25) with prenyltributyltin, Claisen-Schmidt condensation with 4-(methoxymethoxy)benzaldehyde to form the triply MOM-protected prenylchalcone 27 and finally deprotection with 2 M HCl in methanol to form isobavachalcone in an overall yield of 15 % over five steps. The X-ray crystal structures of 2,4-dihydroxy-3-iodoacetophenone (21) and of several prenylated chalcones are reported, including the elucidation of their hydrogen-bonding networks in the solid state. The synthetic route has been extended to include organometallic derivatives in which the 4-(methoxymethoxy) benzaldehyde used in the Claisen-Schmidt condensation has been replaced by formylferrocene, formylruthenocene or (η5-formylcyclopentadienyl) (η4-tetraphenylcyclobutadiene)cobalt to form the corresponding analogues of isobavachalcone containing organometallic sandwich moieties.
- Grealis, John P.,Mueller-Bunz, Helge,Ortin, Yannick,Casey, Michael,McGlinchey, Michael J.
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p. 332 - 347
(2013/03/13)
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- Synthesis and antibacterial activity of chalcones bearing prenyl or geranyl groups from Angelica keiskei
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Chalcones bearing prenyl or geranyl groups from Angelica keiskei, such as 4-hydroxyderricin (1a), xanthoangelol (1e), xanthoangelol F (1f), xanthoangelol H (2), deoxyxanthoangelol H (3), and deoxydihydroxanthoangelol H (4) and their derivatives were synthesized. From the evaluation of antibacterial activity of the synthesized chalcones, 1a, isobavachalcone (1b), 1e, 1f, bavachalcone (5a), and broussochalcone B (5b) were found to inhibit Gram-positive bacteria.
- Sugamoto, Kazuhiro,Matsusita, Yoh-Ichi,Matsui, Kana,Kurogi, Chiaki,Matsui, Takanao
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p. 5346 - 5359
(2011/08/04)
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