Synthesis of Cardiopetaline via a Wagner–Meerwein Rearrangement without Preactivation of the Pivotal Hydroxy Group

Nishiyama, Yoshitake; Yokoshima, Satoshi; Fukuyama, Tohru

doi:10.1021/acs.orglett.7b02812

Cited by 34 publications

(14 citation statements)

References 35 publications

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“…DAs, whether C 18 , C 19 , or C 20 , are all presumed to be derived from the kaurane and atisane diterpenoid families 5 , 6 , 7 . That is, C 20 atisane and kaurane serve as biosynthetic precursors to C 18 - and C 19 -DAs, a mechanism proven by total synthesis 8 , 9 . Thereby, the biosynthesis of DAs undergoes two principal phases.…”

Section: Introductionmentioning

confidence: 99%

Functional identification of the terpene synthase family involved in diterpenoid alkaloids biosynthesis in Aconitum carmichaelii

Mao

Jin

Chen

et al. 2021

Acta Pharmaceutica Sinica B

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Aconitum carmichaelii is a high-value medicinal herb widely used across China, Japan, and other Asian countries. Aconitine-type diterpene alkaloids (DAs) are the characteristic compounds in Aconitum . Although six transcriptomes, based on short-read next generation sequencing technology, have been reported from the Aconitum species, the terpene synthase (TPS) corresponding to DAs biosynthesis remains unidentified. We apply a combination of Pacbio isoform sequencing and RNA sequencing to provide a comprehensive view of the A. carmichaelii transcriptome. Nineteen TPSs and five alternative splicing isoforms belonging to TPS-b, TPS-c, and TPS-e/f subfamilies were identified . In vitro enzyme reaction analysis functional identified two sesqui-TPSs and twelve diTPSs. Seven of the TPS-c subfamily genes reacted with GGPP to produce the intermediate ent -copalyl diphosphate. Five AcKSLs separately reacted with ent -CPP to produce ent -kaurene, ent -atiserene, and ent -13- epi -sandaracopimaradie: a new diterpene found in Aconitum . AcTPSs gene expression in conjunction DAs content analysis in different tissues validated that ent -CPP is the sole precursor to all DAs biosynthesis, with AcKSL1, AcKSL2s and AcKSL3-1 responsible for C 20 atisine and napelline type DAs biosynthesis, respectively. These data clarified the molecular basis for the C 20 -DAs biosynthetic pathway in A. carmichaelii and pave the way for further exploration of C 19 -DAs biosynthesis in the Aconitum species.

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Section: Introductionmentioning

confidence: 99%

Functional identification of the terpene synthase family involved in diterpenoid alkaloids biosynthesis in Aconitum carmichaelii

Mao

Jin

Chen

et al. 2021

Acta Pharmaceutica Sinica B

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“…To determine the appropriate conditions for DHAP, a model reaction involving the coupling between PhI and dibromobithiophene was carried out under eight sets of conditions. Because pivalic acid (PivOH) played a key role in DHAP [ 62 , 63 , 64 ], the reaction conditions for all DHAP involved PivOH as the additive and anhydrous toluene as the solvent. So we choose the different palladium catalysts, bases and phosphine ligands to explore the optimal reaction condition.…”

Section: Methodsmentioning

confidence: 99%

Novel Conjugated Polymers Prepared by Direct (Hetero) arylation: An Eco-Friendly Tool for Organic Electronics

et al. 2018

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The phthalimide (PhI) moiety has been attracting more attention as an excellent acceptor building block in donor-acceptor (D-A) conjugated polymers. In this paper; three D-A conjugated polymers with or without thiocarbonyl moieties are successfully prepared by the direct (hetero)-arylation polymerization (DHAP), which is an atom efficient and facile synthetic strategy to obtain polymer materials. Compared with the traditional carbon-carbon coupling reactions, this method possesses more advantages, including: fewer synthetic steps, avoidance of the preparation of the organometallic reagents, higher atom economy and fewer toxic byproducts, better compatibility with chemically sensitive functional groups and so on. All three of these designed PhI-based polymers exhibited favourable optoelectronic and thermal performance. The optical, thermodynamic and electrochemical properties of the synthesized polymers were systematically investigated using ultraviolet-visible (UV-vis) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and cyclic voltammetry (CV). The results of these three polymers indicated that thionation of the carbonyl was a highly effective methods to improve the properties of PhI-based polymers; and provided impetus for the development of thionated PhI derivatives for organic electronic applications.

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“…The value of such rearrangements is difficult to dene; however, they can provide the ability to trace back a complex bridged framework to a more readily accessible one and have been used in other diterpenoid alkaloid syntheses. 18,[41][42][43][44][45] In the case of the Li synthesis of the arcutanetype alkaloids, the bioinspired rearrangement is central to what is the shortest reported syntheses to date. That said, bioinspired syntheses and retrosyntheses borne out of bond-network analysis are not necessarily mutually exclusive; Li's rearrangement forges the maximally bridged ring at a late stage and all other disconnections follow the tenets of bond-network analysis.…”

Section: (2019)mentioning

confidence: 99%

Retrosynthetic strategies and their impact on synthesis of arcutane natural products

2020

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Synthesis of Cardiopetaline via a Wagner–Meerwein Rearrangement without Preactivation of the Pivotal Hydroxy Group

Cited by 34 publications

References 35 publications

Functional identification of the terpene synthase family involved in diterpenoid alkaloids biosynthesis in Aconitum carmichaelii

Functional identification of the terpene synthase family involved in diterpenoid alkaloids biosynthesis in Aconitum carmichaelii

Novel Conjugated Polymers Prepared by Direct (Hetero) arylation: An Eco-Friendly Tool for Organic Electronics

Retrosynthetic strategies and their impact on synthesis of arcutane natural products

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