Straightforward Acid‐Catalyzed Synthesis of Pyrrolyldipyrromethenes

Yu, Changjiang; Jiao, Lijuan; Tan, Xujun; Wang, Jun; Xu, Yajun; Wu, Yangchun; Yang, Gaosheng; Wang, Zhaoyun; Hao, Erhong

doi:10.1002/anie.201202850

Cited by 35 publications

(13 citation statements)

References 61 publications

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“… 9 The copper center is closer to the dipyrrin unit and the Cu–N bond distance to pyrrole ring A (1.931(9) Å) is longer than those to rings B and C (1.909(8) and 1.900(8) Å, respectively). In addition, C–N and C–C bond metric comparisons with free pyrrolyldipyrrin ligands 26 , 36 , 47 , 48 and with Zn(II) complex Zn(HPD1) 2 confirm a fully conjugated tripyrrolic scaffold in Cu(PD1). Such considerations, together with the absence of counterions, indicate that Cu(II) ions bind to deprotonated ligand PD1 2– without complications arising from interfering redox events.…”

Section: Resultsmentioning

confidence: 90%

Prodigiosin Analogue Designed for Metal Coordination: Stable Zinc and Copper Pyrrolyldipyrrins

et al. 2014

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The pyrrolyldipyrrin motif is found in several naturally occurring prodigiosin pigments. The potential roles of the interactions of prodigiosins with transition metals and the properties of metal-bound pyrrolyldipyrrins, however, have been difficult to assess because of the very limited number of well-characterized stable complexes. Here, we show that the introduction of a meso-aryl substituent and an ethyl ester group during the sequential assembly of the three heterocycles affords a pyrrolyldipyrrin of enhanced coordinating abilities when compared to that of natural prodigiosins. UV–visible absorption studies indicate that this ligand promptly binds Zn(II) ions with 2:1 ligand-to-metal stoichiometry and Cu(II) ions with 1:1 stoichiometry. Notably, no addition of base is required for the formation of the resulting stable complexes. The crystal structures reveal that whereas the tetrahedral zinc center engages two nitrogen donors on each ligand, the pseudosquare planar copper complex features coordination of all three pyrrolic nitrogen atoms and employs the ester group as a neutral ligand. This first example of coordination of a redox-active transition metal within a fully conjugated pyrrolyldipyrrin framework was investigated spectroscopically by electron paramagnetic resonance to show that the 1:1 metal-to-ligand ratio found in the crystal structure is also maintained in solution.

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Section: Resultsmentioning

confidence: 90%

Prodigiosin Analogue Designed for Metal Coordination: Stable Zinc and Copper Pyrrolyldipyrrins

et al. 2014

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“…In order to enable accurate analysis of prodigiosin in P. putida , we chemically synthesized the compound as a reference. Thus, a shortened synthesis route was developed based on published protocols ( Trofimov et al, 1985 ; Hajipour et al, 1999 ; Dairi et al, 2006 ; Durchschein et al, 2010 ; Yu et al, 2012 ). The two biomimetic intermediates MAP and MBC were combined to prodigiosin in a final condensing reaction (see supplementary information 1 and Supplementary Figures S2–S4 for details on prodigiosin synthesis).…”

Section: Resultsmentioning

confidence: 99%

Efficient recombinant production of prodigiosin in Pseudomonas putida

et al. 2015

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Serratia marcescens and several other bacteria produce the red-colored pigment prodigiosin which possesses bioactivities as an antimicrobial, anticancer, and immunosuppressive agent. Therefore, there is a great interest to produce this natural compound. Efforts aiming at its biotechnological production have so far largely focused on the original producer and opportunistic human pathogen S. marcescens. Here, we demonstrate efficient prodigiosin production in the heterologous host Pseudomonas putida. Random chromosomal integration of the 21 kb prodigiosin biosynthesis gene cluster of S. marcescens in P. putida KT2440 was employed to construct constitutive prodigiosin production strains. Standard cultivation parameters were optimized such that titers of 94 mg/L culture were obtained upon growth of P. putida at 20°C using rich medium under high aeration conditions. Subsequently, a novel, fast and effective protocol for prodigiosin extraction and purification was established enabling the straightforward isolation of prodigiosin from P. putida growth medium. In summary, we describe here a highly efficient method for the heterologous biosynthetic production of prodigiosin which may serve as a basis to produce large amounts of this bioactive natural compound and may provide a platform for further in-depth studies of prodiginine biosynthesis.

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“…Synthesis of pyrrolyldipyrromethenes 26 from 5-halogenated 2-acylpyrroles as detailed by Hao, et al . [34] …”

Section: Methodsmentioning

confidence: 99%

“…In pursuit of new methods for the facile construction of prodigiosin-type natural products, Hao and co-workers described a one-pot synthesis of pyrrolyldipyrromethenes from 5-halogenated-2-formylpyrrole (Scheme 5). [34] This synthesis relies on the use of POCl 3 to generate an intermediate 9-halodipyrromethene 25 , which readily undergoes nucleophilic aromatic substitution to yield the target pyrrolyldipyrromethenes 26 in 41–79 % yield. Mechanistic studies supported the intermediacy of a 9-halodipyrromethene 25 that undergoes a subsequent S N Ar reacton with pyrrole to yield the corresponding pyrrolyldipyrromethenes in 51–90 % yield.…”

Section: Synthesis Of 22’-bipyrrolesmentioning

confidence: 99%

Functionalized 2,2’-Bipyrroles: Building Blocks for Pyrrolic Macrocycles

Anguera¹,

Brewster²,

Sánchez‐García³

et al. 2018

MHC

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Functionalized N-unsubstituted 2,2’-bipyrroles are basic building blocks for the preparation of pyrrolic macrocycles and natural products, such as prodigiosines. The aim of this review is to provide a description of the most important methodologies used to prepare 2,2’-bipyrroles and their central role as building blocks for the synthesis of porphyrinoids and property-defining structural elements therein.

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Straightforward Acid‐Catalyzed Synthesis of Pyrrolyldipyrromethenes

Cited by 35 publications

References 61 publications

Prodigiosin Analogue Designed for Metal Coordination: Stable Zinc and Copper Pyrrolyldipyrrins

Prodigiosin Analogue Designed for Metal Coordination: Stable Zinc and Copper Pyrrolyldipyrrins

Efficient recombinant production of prodigiosin in Pseudomonas putida

Functionalized 2,2’-Bipyrroles: Building Blocks for Pyrrolic Macrocycles

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