Total Synthesis of Tryprostatins A and B

Yamakawa, Takayuki; Ideue, Eiji; Shimokawa, Jun; Fukuyama, Tohru

doi:10.1002/ange.201004963

Cited by 8 publications

(2 citation statements)

References 44 publications

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“…Allylierung und Prenylierung von 1‐Phenyl‐1 H ‐pyrazol waren ebenso möglich, jedoch in geringeren Ausbeuten. Außerdem gelang uns die herausfordernde C2‐selektive Allylierung von Indolen16 mithilfe der abtrennbaren dirigierenden Gruppe Pyrimidyl. Bei Einsatz des phenylsubstituierten Carbonates 2 e wurde jedoch ein nichttrennbares Gemisch von C2‐ und C3‐allyliertem Produkt erhalten.…”

Section: Methodsunclassified

Density Functional Theory Study of trans‐Dioxo Complexes of Iron, Ruthenium, and Osmium with Saturated Amine Ligands, trans‐[M(O)₂(NH₃)₂(NMeH₂)₂]²⁺ (M=Fe, Ru, Os), and Detection of [Fe(qpy)(O)₂]ⁿ⁺ (n=1, 2) by High‐Resolution ESI Mass Spectrometry

Tong

Wong

Che

2008

Chemistry A European J

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Density functional theory (DFT) calculations on trans-dioxo metal complexes containing saturated amine ligands, trans-[M(O)2(NH3)2(NMeH2)2]2+ (M=Fe, Ru, Os), were performed with different types of density functionals (DFs): 1) pure generalized gradient approximations (pure GGAs): PW91, BP86, and OLYP; 2) meta-GGAs: VSXC and HCTH407; and 3) hybrid DFs: B3LYP and PBE1PBE. With pure GGAs and meta-GGAs, a singlet d2 ground state for trans-[Fe(O)2(NH3)2(NMeH2)2]2+ was obtained, but a quintet ground state was predicted by the hybrid DFs B3LYP and PBE1PBE. The lowest transition energies in water were calculated to be at lambda approximately 509 and 515 nm in the respective ground-state geometries from PW91 and B3LYP calculations. The nature of this transition is dependent on the DFs used: a ligand-to-metal charge-transfer (LMCT) transition with PW91, but a pi(Fe-O)-->pi*(Fe-O) transition with B3LYP, in which pi and pi* are the bonding and antibonding combinations between the dpi(Fe) and ppi(O(2-)) orbitals. The FeVI/V reduction potential of trans-[Fe(O)2(NH3)2NMeH2)2]2+ was estimated to be +1.30 V versus NHE based on PW91 results. The [Fe(qpy)(O)2](n+) (qpy=2,2':6',2'':6'',2''':6''',2''''-quinquepyridine; n=1 and 2) ions, tentatively assigned to dioxo iron(V) and dioxo iron(VI), respectively, were detected in the gas phase by high-resolution ESI-MS spectroscopy.

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Section: Methodsunclassified

Density Functional Theory Study of trans‐Dioxo Complexes of Iron, Ruthenium, and Osmium with Saturated Amine Ligands, trans‐[M(O)₂(NH₃)₂(NMeH₂)₂]²⁺ (M=Fe, Ru, Os), and Detection of [Fe(qpy)(O)₂]ⁿ⁺ (n=1, 2) by High‐Resolution ESI Mass Spectrometry

Tong

Wong

Che

2008

Chemistry A European J

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“…Therefore, different approaches and agents were developed for synthesis of the prenylated indole derivatives. Prenyl bromide, isoprenyl bromide or prenyl acetate with NaH,10 lithium salt9 or other metal catalysts11 are often used in the prenylation reactions. However, chemical prenylation usually has some limitations such as different reactivities of C‐atoms on the indole nucleus, low selectivity of the prenylation for several positions, side products, toxicity and danger of the reagents and solvents for products and environment.…”

Section: Introductionmentioning

confidence: 99%

Characterization of the molecular differences between ovarian endometrioid carcinoma and ovarian serous carcinoma

Madore

Ren

Filali‐Mouhim

et al. 2009

The Journal of Pathology

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The histopathological diagnosis of high-grade endometrioid and serous carcinoma of the ovary is poorly reproducible under the current morphology based classification system, especially for anaplastic, high-grade tumours. The transcription factor Wilms' tumour-1 (WT1) is differentially expressed among the gynaecological epithelia from which epithelial ovarian cancers (EOCs) are believed to originate. In EOCs, WT1 protein is observed in the majority of serous carcinomas and in up to 30% of endometrioid carcinomas. It is unclear whether the latter is a reflection of the actual incidence of WT1 protein expression in endometrioid carcinomas, or whether a significant number of high-grade serous carcinomas have been misclassified as endometrioid carcinoma. Several genetic aberrations are reported to occur in EOCs. These include mutation of the TP53 gene, aberrant activation of beta-catenin signalling and loss of PTEN protein expression, among others. It is unclear whether these aberrations are histotype-specific. The aim of this study was to better define the molecular characteristics of serous and endometrioid carcinomas in an attempt to address the problems with the current histopathological classification methods. Gene expression profiles were analysed to identify reproducible gene expression phenotypes for endometrioid and serous carcinomas. Tissue microarrays (TMA) were used to assess the incidence of TP53, beta-catenin and PTEN aberrations in order to correlate their occurrence with WT1 as an immunohistochemistry based biomarker of serous histotype. It was found that nuclear WT1 protein expression can identify misclassified high-grade endometrioid carcinomas and these tumours should be reassigned to serous histotype. Although low-grade endometrioid carcinomas rarely progress to high-grade carcinomas, a combined WT1-negative, TP53-positive immunophenotype may identify an uncommon high-grade subtype of ovarian endometrioid carcinoma. GEO database: array data accession number GSE6008.

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One Substrate – Seven Products with Different Prenylation Positions in One‐Step Reactions: Prenyltransferases Make it Possible

Fan

2013

Adv Synth Catal

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Prenylated indole alkaloids derived from L‐tryptophan are widely distributed in nature and show diverse biological and pharmacological activities, usually distinct from their non‐prenylated precursors. Prenyltransferases catalyze the transfer reactions of prenyl moieties onto the indole nucleus and contribute largely to the structural diversity of these compounds. In this study, we demonstrate the acceptance of cyclo‐L‐homotryptophan‐D‐valine, an unnatural cyclic dipeptide, by eight prenyltransferases of the dimethylallyltryptophan synthase superfamily. Seven products with one prenyl moiety at each position of the indole nucleus and one diprenylated derivative were isolated from enzyme assays of cyclo‐L‐homotryptophan‐D‐valine with dimethylallyl diphosphate. To the best of our knowledge, this is the first report for production of seven monoprenylated products from one substrate by one‐step reactions.magnified image

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Total Synthesis of Tryprostatins A and B

Cited by 8 publications

References 44 publications

Density Functional Theory Study of trans‐Dioxo Complexes of Iron, Ruthenium, and Osmium with Saturated Amine Ligands, trans‐[M(O)₂(NH₃)₂(NMeH₂)₂]²⁺ (M=Fe, Ru, Os), and Detection of [Fe(qpy)(O)₂]ⁿ⁺ (n=1, 2) by High‐Resolution ESI Mass Spectrometry

Density Functional Theory Study of trans‐Dioxo Complexes of Iron, Ruthenium, and Osmium with Saturated Amine Ligands, trans‐[M(O)₂(NH₃)₂(NMeH₂)₂]²⁺ (M=Fe, Ru, Os), and Detection of [Fe(qpy)(O)₂]ⁿ⁺ (n=1, 2) by High‐Resolution ESI Mass Spectrometry

Characterization of the molecular differences between ovarian endometrioid carcinoma and ovarian serous carcinoma

One Substrate – Seven Products with Different Prenylation Positions in One‐Step Reactions: Prenyltransferases Make it Possible

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Total Synthesis of Tryprostatins A and B

Cited by 8 publications

References 44 publications

Density Functional Theory Study of trans‐Dioxo Complexes of Iron, Ruthenium, and Osmium with Saturated Amine Ligands, trans‐[M(O)2(NH3)2(NMeH2)2]2+ (M=Fe, Ru, Os), and Detection of [Fe(qpy)(O)2]n+ (n=1, 2) by High‐Resolution ESI Mass Spectrometry

Density Functional Theory Study of trans‐Dioxo Complexes of Iron, Ruthenium, and Osmium with Saturated Amine Ligands, trans‐[M(O)2(NH3)2(NMeH2)2]2+ (M=Fe, Ru, Os), and Detection of [Fe(qpy)(O)2]n+ (n=1, 2) by High‐Resolution ESI Mass Spectrometry

Characterization of the molecular differences between ovarian endometrioid carcinoma and ovarian serous carcinoma

One Substrate – Seven Products with Different Prenylation Positions in One‐Step Reactions: Prenyltransferases Make it Possible

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Density Functional Theory Study of trans‐Dioxo Complexes of Iron, Ruthenium, and Osmium with Saturated Amine Ligands, trans‐[M(O)₂(NH₃)₂(NMeH₂)₂]²⁺ (M=Fe, Ru, Os), and Detection of [Fe(qpy)(O)₂]ⁿ⁺ (n=1, 2) by High‐Resolution ESI Mass Spectrometry

Density Functional Theory Study of trans‐Dioxo Complexes of Iron, Ruthenium, and Osmium with Saturated Amine Ligands, trans‐[M(O)₂(NH₃)₂(NMeH₂)₂]²⁺ (M=Fe, Ru, Os), and Detection of [Fe(qpy)(O)₂]ⁿ⁺ (n=1, 2) by High‐Resolution ESI Mass Spectrometry