Synthesis of the Ring C Pyrrole of Native Chlorophylls and Bacteriochlorophylls

Wang, Pengzhi; Nguyen, Khiem Chau; Lindsey, Jonathan S.

doi:10.1021/acs.joc.9b01650

Cited by 16 publications

(26 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…S6) allowed identification of 3-acetyl-4-methylpyrrole for the compound at 16.05 min. All of these data are in accordance with the literature ( 33 – 35 ). Thus, deletion of PaNsdD in both wild-type and ΔPaStcA background almost completely blocked the production of 3-acetyl-4-methylpyrrole (at 16.05 min), implying that PaNsdD positively regulates its biosynthesis.…”

Section: Resultssupporting

confidence: 92%

See 1 more Smart Citation

Functional Characterization of the GATA-Type Transcription Factor PaNsdD in the Filamentous Fungus Podospora anserina and Its Interplay with the Sterigmatocystin Pathway

Shen

Gaslonde

Roullier

et al. 2022

Appl Environ Microbiol

View full text Add to dashboard Cite

The model ascomycete Podospora anserina , featured by its strict sexual development, is a prolific but yet unexploited reservoir of natural products. The GATA-type transcription factor NsdD has been characterized by the role in balancing asexual and sexual reproduction, and governing secondary metabolism in filamentous fungi. In the present study, we functionally investigated the NsdD ortholog PaNsdD in P. anserina . Compared to the wild-type strain, vegetative growth, ageing processes, sexual reproduction, stress tolerance and interspecific confrontations in the mutant were drastically impaired, owing to the loss of function of PaNsdD. In addition, the production of 3-acetyl-4-methylpyrrole, a new metabolite identified in P. anserina in this study, was significantly inhibited in the ΔPaNsdD mutant. We also demonstrated the interplay of PaNsdD with the sterigmatocystin biosynthetic gene pathway, especially as the deletion of PaNsdD triggered the enhanced red-pink pigment biosynthesis that only occurs in the presence of the core polyketide synthase-encoding gene PaStcA of the sterigmatocystin pathway. Taken together, these results contribute to a better understanding of the global regulation mediated by PaNsdD in P. anserina , especially with regard to its unexpected involvement in fungal ageing process and its interplay with sterigmatocystin pathway. Importance Fungal transcription factors play an essential role in coordinating multiple physiological processes. Yet, little is known about the functional characterization of transcription factors in the filamentous fungus P. anserina . In this study, a GATA-type regulator PaNsdD was investigated in P. anserina . The results showed that PaNsdD was a key factor that can control the fungal ageing process, vegetative growth, pigmentation, stress response, interspecific confrontations, and positively regulate the production of 3-acetyl-4-methylpyrrole. Meanwhile, a molecular interaction was implied between PaNsdD and the sterigmatocystin pathway. Overall, loss of function of PaNsdD seems to be highly disadvantageous for P. anserina , which relies on pure sexual reproduction in limited lifespan. Therefore, PaNsdD is clearly indispensable for the survival and propagation of P. anserina in its complex ecological niches.

show abstract

Section: Resultssupporting

confidence: 92%

“…Fractions containing the products were pooled, and the mobile phase was evaporated under reduced pressure to furnish 1.9 mg of the desired pure compound. NMR and MS data of this metabolite were in accordance with the literature ( 33 , 34 ) and were permitted to identify the product as 3-acetyl-4-methylpyrrole.…”

Section: Methodsmentioning

confidence: 63%

Functional Characterization of the GATA-Type Transcription Factor PaNsdD in the Filamentous Fungus Podospora anserina and Its Interplay with the Sterigmatocystin Pathway

Shen

Gaslonde

Roullier

et al. 2022

Appl Environ Microbiol

View full text Add to dashboard Cite

show abstract

“…The organic extract was dried (Na 2 SO 4 ) and concentrated to a yellow oil. Chromatography [silica, hexanes/ethyl acetate (3:1) to ethyl acetate] afforded a colorless oil (13.2 g, 35%): 1 tert-Butyl (4-Nitrophenyl)glutarate (8). A solution of 7 (8.46 g, 45.0 mmol) in anhydrous THF (135 mL) was treated with 4nitrophenol (6.88 g, 49.5 mmol) and DCC (13.9 g, 67.5 mmol) under argon at 0 °C.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…A current objective is to adapt the general synthesis to accommodate the substituents characteristic of the native macrocycles. To date, we have synthesized the ring C pyrrole, 8 shown that stereodefined model substituents (17-methyl, 18-ethyl) in ring D can be incorporated at an early stage of the synthesis and carried through Knoevenagel and double-ring closure processes to form the macrocycle without loss of stereochemical integrity, 9 refined the conditions for the double-ring closure, 10 compounds containing a 3-acetyl as well as other substituents. 11 The prior incorporation of an acetyl 11 or carboethoxy 9,10 group at the 3-position in each case required independent synthesis beginning with the corresponding substituted pyrrole.…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis of AD-Dihydrodipyrrins Equipped with Latent Substituents of Native Chlorophylls and Bacteriochlorophylls

Wang

Lindsey

2021

J. Org. Chem.

Self Cite

View full text Add to dashboard Cite

Native chlorophylls and bacteriochlorophylls share a common trans-substituted pyrroline ring D (17-propionic acid, 18-methyl), whereas diversity occurs in ring A particularly at the 3-position. Two dihydrodipyrrins equipped with native-like D-ring substituents and tailorable A-ring substituents have been synthesized. The synthesis relies on a Schreiber-modified Nicholas reaction to construct the stereochemically defined precursor to ring D, a dialkyl-substituted pent-4-ynoic acid. The carboxylic acid group of the intact propionic acid proved unworkable, whereupon protected propionate (−CO2 tBu) and several latent propyl ethers were examined. The tert-butyldiphenylsilyl-protected propanol substituent proved satisfactory for reaction of the chiral N-acylated oxazolidinone, affording (2S,3S)-2-(3-((tert-butyldiphenylsilyl)oxy)propyl)-3-methylpent-4-ynoic acid in ∼30% yield over 8 steps. Two variants for ring A, 2-tert-butoxycarbonyl-3-Br/H-5-iodo-4-methylpyrrole, were prepared via the Barton–Zard route. Dihydrodipyrrin formation from the pyrrole and pentynoic acid entailed Jacobi Pd-mediated lactone formation, Petasis methenylation, and Paal–Knorr-type pyrroline formation. The two AD-dihydrodipyrrins bear the D-ring methyl and protected propanol groups with a stereochemical configuration identical to that of native (bacterio)chlorophylls, and a bromine or no substitution in ring A corresponding to the 3-position of (bacterio)chlorophylls. The analogous β-position of a lactone–pyrrole intermediate on the path to the dihydrodipyrrin also was successfully brominated, opening opportunities for late-stage diversification in the synthesis of (bacterio)chlorophylls.

show abstract

“…Pyrroles, π-excess N-heterocyclic systems, are found in nature, and several derivatives with interesting properties have been synthesized [1][2][3][4][5]. Because of the importance of pyrrole and its substituted derivatives as basic substructures in natural and synthetic products, the synthesis of these five-membered heterocycles is of interest to researchers.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 3-Aroyl-4-heteroarylpyrrole Derivatives by the Van Leusen Method

Trilleras

Quiroga

Hormaza

2022

Molbank

View full text Add to dashboard Cite

The synthesis and structural diversification of N-heterocycles systems have attracted much attention because of their potential applications. Three 6-aryl-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine-5-carbaldehyde 4 derivatives, in reaction with acetophenones 5, via conventional Claisen–Schmidt condensation reactions, generated the respective enones. The enones were used as electron-deficient olefins in a “formal” [2+3] cycloaddition reaction using p-tosylmethyl isocyanide—TosMIC 7. This protocol allows access to 3-(substituted aroyl)-4-heteroaryl pyrrole derivatives by the Van Leusen method.

show abstract

Synthesis of the Ring C Pyrrole of Native Chlorophylls and Bacteriochlorophylls

Cited by 16 publications

References 24 publications

Functional Characterization of the GATA-Type Transcription Factor PaNsdD in the Filamentous Fungus Podospora anserina and Its Interplay with the Sterigmatocystin Pathway

Functional Characterization of the GATA-Type Transcription Factor PaNsdD in the Filamentous Fungus Podospora anserina and Its Interplay with the Sterigmatocystin Pathway

Synthesis of AD-Dihydrodipyrrins Equipped with Latent Substituents of Native Chlorophylls and Bacteriochlorophylls

Synthesis of 3-Aroyl-4-heteroarylpyrrole Derivatives by the Van Leusen Method

Contact Info

Product

Resources

About