Monomeric Dihydroanthraquinones: A Chemoenzymatic Approach and its (Bio)synthetic Implications for Bisanthraquinones

Saha, Nirmal; Mondal, Amit; Witte, Karina; Singh, Savitri; Müller, Michael; Husain, Syed Masood

doi:10.1002/chem.201705998

Cited by 15 publications

(33 citation statements)

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“…Hence, the results obtained here confirm the optical purity of these complex dimeric compounds to be > 99 % ee . (Figure ) . In addition, we are hopeful that the method developed here will have major implications on the identification of new enzymes which can give ( S )‐configured dihydroanthracenones as well as the natural products such as (+)‐rugulosin ( 6 ) and (+)‐2,2'‐ epi ‐cytoskyrin A ( 7 ) and related metabolites that can be synthesized using such dihydroanthracenones.…”

Section: Figurementioning

confidence: 99%

“…Other enzymes which also catalyze the same transformation include PHAR of Cochliobolus lunatus , AflM of Aspergillus parasiticus and ARti (anthrol reductase) of Talaromyces islandicus . Moreover, the utilization of ( R )‐ 9 (synthesized chemoenzymatically using PHAR) in the biomimetic synthesis of dimeric bisanthraquinone, (–)‐rugulosin ( 10 ) signifies its role as a putative biosynthetic precursor (Figure b) …”

Section: Figurementioning

confidence: 99%

“…(a) Total synthesis of ( S )‐configured dihydroanthracenones 4 , 5 and modified bisanthraquinones 6 , 7 . (b) Chemoenzymatic synthesis of ( R )‐3,4‐dihydroanthracenone 9 and (–)‐rugulosin ( 10 ) . (c) Synthesis of racemic dihydroanthracenones using NaBH 4 .…”

Section: Figurementioning

confidence: 99%

“…In addition, we synthesized both ( R )‐ 16 and ( R )‐ 19 by employing a chemoenzymatic procedure using MdpC of A. nidulans as well as PHAR of C. lunatus , , . The enzymatically reduced products ( R )‐ 16 and ( R )‐ 19 , were then analyzed for their enantiopurity in comparison with rac ‐ 16 and rac ‐ 19 using chiral HPLC.…”

Section: Figurementioning

confidence: 99%

“…Dihydroanthraquinones ( 20 , 21 ) and modified bisanthraquinones ( 22 , 23 , 10 , ent ‐ 7 ) reportedly synthesized through chemoenzymatic strategy using PHAR of C. lunatus …”

Section: Figurementioning

confidence: 99%

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A Biomimetic Synthesis of Racemic Dihydroanthracen‐1(2H)‐ones Using Sodium Borohydride in Water

et al. 2020

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Herein, we report a single step synthesis of racemic dihydroanthracenones by the reduction of anthraquinones using NaBH 4 and Na 2 S 2 O 4 in water. The racemic mixture is utilized to determine the enantiomeric excess for the chiral dihydroanthracenones reportedly synthesized by the chemoenzymatic reduction of anthraquinones. The results show > 99% ee for the Dihydroanthracenones are recognised as putative biosynthetic precursors involved in the biosynthesis of deoxyanthraquinones and modified bisanthraquinones in fungi. [1,2] Despite not being isolated from natural sources as yet, the chiral dihydroanthracenones are synthesized using two completely different approaches and are used in the synthesis of modified bisanthraquinones. In the very first approach, Nicolaou and coworkers achieved the total synthesis of protected (S)-configured dihydroanthracenones 4, 5 by the Hauser annulation between MOM protected nitrile 1 or 2 and MOM protected enone 3, respectively (Figure 1a). [3,4] Both 4 and 5 are then being used as precursors towards the synthesis of naturally occurring dimeric bisanthraquinones, (+)-rugulosin (6) and (+)-2,2′-epi-cytoskyrin A (7) (Figure 1a). [3] However, the requirement of a large number of steps to synthesize 1-3 involving extensive protection and deprotection of hydroxyl groups makes this approach less attractive for the synthesis of dihydroanthracenones. As an alternate Müller and co-workers have identified a fungal enzyme, MdpC of Aspergillus nidulans, using which the putative biosynthetic intermediates, (R)-configured dihydroanthracenones were synthesized chemoenzymatically using anthraquinones. [5] For example, (R)-3,8,9,10-tetrahydroxy-6-methyl-3,4-dihydroanthracen-1(2H)-one (9) is synthesized by MdpC-catalyzed reduction of emodin hydroquinones 13a/13b [formed in situ by the reduction of emodin (8) in the presence of Na 2 S 2 O 4 ] using NADPH as a cofactor in buffer (Figure 1b). [5] Other enzymes which also catalyze the same transformation include PHAR of Cochliobolus [a] A.Scheme 2. Proposed retrosynthetic route for the preparation of racemic dihydroanthracenones based on the procedure reported by Nicolaou and co-workers. [3] Eur.

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Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

“…Dihydroanthraquinones ( 20 , 21 ) and modified bisanthraquinones ( 22 , 23 , 10 , ent ‐ 7 ) reportedly synthesized through chemoenzymatic strategy using PHAR of C. lunatus …”

Section: Figurementioning

confidence: 99%

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A Biomimetic Synthesis of Racemic Dihydroanthracen‐1(2H)‐ones Using Sodium Borohydride in Water

et al. 2020

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Concise chemoenzymatic total synthesis of (−)-rubroskyrin, (−)-deoxyrubroskyrin (−)-luteoskyrin, and (−)-deoxyluteoskyrin

2022

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Dothideomins A–D, Antibacterial Polycyclic Bisanthraquinones from the Endophytic Fungus Dothideomycetes sp. BMC-101

et al. 2022

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Four new bisanthraquinones, dothideomins A–D (1–4), were identified from Dothideomycetes sp. BMC-101, an endophytic fungus isolated from Magnolia grandiflora L. leaves. Their chemical structures were established by NMR analysis, single-crystal X-ray crystallography, and ECD analysis. Dothideomins A–D (1–4) were characterized by an unusual 6/6/6/5/6/3/6/6 octocyclic scaffold (1 and 2) and a 6/6/6/5/6/6/6 heptacyclic scaffold (3 and 4), respectively. All compounds, especially 1 and 3, exhibited potent antibacterial activity with MIC values ranging from 0.4 to 0.8 μg/mL.

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Monomeric Dihydroanthraquinones: A Chemoenzymatic Approach and its (Bio)synthetic Implications for Bisanthraquinones

Cited by 15 publications

References 45 publications

A Biomimetic Synthesis of Racemic Dihydroanthracen‐1(2H)‐ones Using Sodium Borohydride in Water

A Biomimetic Synthesis of Racemic Dihydroanthracen‐1(2H)‐ones Using Sodium Borohydride in Water

Concise chemoenzymatic total synthesis of (−)-rubroskyrin, (−)-deoxyrubroskyrin (−)-luteoskyrin, and (−)-deoxyluteoskyrin

Dothideomins A–D, Antibacterial Polycyclic Bisanthraquinones from the Endophytic Fungus Dothideomycetes sp. BMC-101

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