Total Syntheses of (±)-α-Lycorane and (±)-1-Deoxylycorine

Jung, Yong Geun; Lee, Sang Choul; Cho, Hyun Kyu; Darvatkar, Nitin B.; Song, Junesol; Cho, Cheon‐Gyu

doi:10.1021/ol303157b

Cited by 38 publications

(17 citation statements)

References 30 publications

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“…Then, 1 was converted into 16 , which was reduced with LiAlH 4 to afford (+)‐α‐lycorane. All of the spectroscopic data for synthetic (+)‐α‐lycorane were in accordance with the data reported previously 11j. There are three elegant asymmetric total syntheses or formal syntheses of (−)‐α‐lycorane to date,12, 3f, g however, their applications to the synthesis of the more complex alkaloid, lycorine, remained unknown.…”

Section: Resultssupporting

confidence: 86%

Catalytic Asymmetric Assembly of Octahydroindolones: Divergent Synthesis of Lycorine‐type Amaryllidaceae Alkaloids (+)‐α‐Lycorane and (+)‐Lycorine

Sun

Zhou

et al. 2014

Chemistry A European J

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We report the first catalytic asymmetric approach to octahydroindolones and a divergent enantioselective synthesis of perhydroindole alkaloids, as exemplified by lycorine-type Amaryllidaceae alkaloids (+)-α-lycorane and (+)-lycorine, from a common intermediate by using a highly concise route. The assembly of octahydroindolones employs a catalytic enantioselective 1,4-conjugate addition of nitro dienynes, followed by a TsOH-catalyzed cascade synthesis of highly functionalized enones, and a diastereoselective intramolecular Michael addition.

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Section: Resultssupporting

confidence: 86%

Catalytic Asymmetric Assembly of Octahydroindolones: Divergent Synthesis of Lycorine‐type Amaryllidaceae Alkaloids (+)‐α‐Lycorane and (+)‐Lycorine

Sun

Zhou

et al. 2014

Chemistry A European J

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“…Norbelladine is methylated by norbelladine 4′- O -methyltransferase (N4OMT) to form 4′- O -methylnorbelladine [23]. The resulting compound is used as an intermediate for the formation of the galantamine, lycorine, a toxic crystalline alkaloid present in many Amaryllidaceae plants [24], and crinamine, one of Amaryllidaceae alkaloids [25]. However, enzymes directly involved in galantamine formation have not been identified yet even though the involvement of cytochrome P450 enzymes (CYP96T1), involved in crinamine formation, has been discussed [26].…”

Section: Introductionmentioning

confidence: 99%

Transcriptome Analysis and Metabolic Profiling of Lycoris Radiata

Park

Yeo

Park

et al. 2019

Biology

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Lycoris radiata belongs to the Amaryllidaceae family and is a bulbous plant native to South Korea, China, and Japan. Galantamine, a representative alkaloid of Amaryllidaceae plants, including L. radiata, exhibits selective and dominant acetylcholinesterase inhibition. In spite of the economic and officinal importance of L. radiata, the molecular biological and biochemical information on L. radiata is relatively deficient. Therefore, this study provides functional information of L. radiata, describe galantamine biosynthesis in the various organs, and provide transcriptomic and metabolic datasets to support elucidation of galantamine biosynthesis pathway in future studies. The results of studies conducted in duplicate revealed the presence of a total of 325,609 and 404,019 unigenes, acquired from 9,913,869,968 and 10,162,653,038 raw reads, respectively, after trimming the raw reads using CutAdapt, assembly using Trinity package, and clustering using CD-Hit-EST. All of the assembled unigenes were aligned to the public databases, including National Center for Biotechnology Information (NCBI) non-redundant protein (NR) and nucleotide (Nt) database, SWISS-PROT (UniProt) protein sequence data bank, The Arabidopsis Information Resource (TAIR), the Swiss-Prot protein database, Gene Ontology (GO), and Clusters of Orthologous Groups (COG) database to predict potential genes and provide their functional information. Based on our transcriptome data and published literatures, eight full-length cDNA clones encoding LrPAL2, LrPAL3, LrC4H2, LrC3H, LrTYDC2, LrNNR, LrN4OMT, and LrCYP96T genes, involved in galantamine biosynthesis, were identified in L. radiata. In order to investigate galantamine biosynthesis in different plant parts of L. radiata grown in a growth chamber, gene expression levels were measured through quantitative real-time polymerase chain reaction (qRT-PCR) analysis using these identified genes and galantamine levels were quantified by high-performance liquid chromatography (HPLC) analysis. The qRT-PCR data revealed high expression levels of LrNNR, LrN4OMT, and LrCYP96T in the bulbs, and, as expected, we observed higher amounts of galantamine in the bulbs than in the root and leaves. Additionally, a total of 40 hydrophilic metabolites were detected in the different organs using gas-chromatography coupled with time-of-flight mass spectrometry. In particular, a strong positive correlation between galantamine and sucrose, which provides energy for the secondary metabolite biosynthesis, was observed.

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“…In 2013, Cho and co‐workers reported a novel synthetic route to two lycorine‐type alkaloids (±)‐α‐lycorane and (±)‐1‐deoxylycorine by utilizing cycloadduct endo ‐ 145 b as the key intermediate readily prepared from the IEDDA reaction of 3,5‐dibromo‐2‐pyrone 140 with styrene 142 b (Scheme 65). [48] The cycloadduct endo ‐ 145 b was subjected to reductive debromination and acidic methanolysis to afford allyl alcohol 286 . Subsequent microwave‐assisted Eschenmoser–Claisen rearrangement of allyl alcohol 286 with 1,1‐dimethoxy‐ N , N ‐dimethylethanamine provided ester 287 which underwent sequential basic hydrolysis and Curtius rearrangement to furnish isocyanate 288 .…”

Section: Applications In Total Synthesismentioning

confidence: 99%

Inverse‐Electron‐Demand Diels–Alder Reactions of 2‐Pyrones: Bridged Lactones and Beyond

Huang

Kouklovsky

Torre

2021

Chemistry A European J

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Inverse‐electron‐demand Diels–Alder (IEDDA) reactions of electron‐poor 2‐pyrones as electrophilic dienes have been extensively studied in the past fifty years. These reactions provide an efficient access to bridged bicyclic lactones and their derivatives, such as densely functionalized 1,3‐cyclohexadienes after CO2 extrusion and polysubstituted aromatic compounds through elimination. This reaction has been used for the synthesis of many biologically active natural products and drug candidates. In this review, the developments of these IEDDA reactions including non‐catalytic, Lewis acid‐catalyzed and organocatalytic IEDDA reactions, and their applications in total synthesis are discussed in detail.

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Total Syntheses of (±)-α-Lycorane and (±)-1-Deoxylycorine

Abstract: New synthetic routes to (±)-α-lycorane and (±)-1-deoxylycorine were exploited. The endo-cycloadduct of 3,5-dibromo-2-pyrone with styrene-type dienophile provided the pivotal intermediate for the syntheses of the titled natural products.

Cited by 38 publications

References 30 publications

Catalytic Asymmetric Assembly of Octahydroindolones: Divergent Synthesis of Lycorine‐type Amaryllidaceae Alkaloids (+)‐α‐Lycorane and (+)‐Lycorine

Catalytic Asymmetric Assembly of Octahydroindolones: Divergent Synthesis of Lycorine‐type Amaryllidaceae Alkaloids (+)‐α‐Lycorane and (+)‐Lycorine

Transcriptome Analysis and Metabolic Profiling of Lycoris Radiata

Inverse‐Electron‐Demand Diels–Alder Reactions of 2‐Pyrones: Bridged Lactones and Beyond

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