Stereoselective Synthesis of (−)‐Chloramphenicol, (+)‐Thiamphenicol and (+)‐Sphinganine via Chiral Tricyclic Iminolactone

Li, Qiong; Li, Chenguang; Xu, Peng‐Fei

doi:10.1002/cjoc.201201093

Cited by 13 publications

(6 citation statements)

References 31 publications

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“…Compound 1 was identified as chloramphenicol based on its spectroscopic data ( Table 1 ) and by comparison of its physical properties with those reported in the literature. Chloramphenicol, first isolated from Streptomyces venezuelae in 1947 [ 10 ], is a natural antibiotic with a relatively broad spectrum of antimicrobial activity [ 11 ]. The structure of compound 2 was elucidated by comparison of its NMR data with those reported previously in the literature.…”

Section: Resultsmentioning

confidence: 99%

Insecticidal Activities of Chloramphenicol Derivatives Isolated from a Marine Alga-Derived Endophytic Fungus, Acremonium vitellinum, against the Cotton Bollworm, Helicoverpa armigera (Hübner) (Lepidoptera: Noctuidae)

et al. 2018

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A great deal of attention has been focused on the secondary metabolites produced by marine endophytic fungi, which can be better alternatives to chemicals, such as biopesticides, for control of polyphagous pests. On the basis of its novel biocontrol attributes, chemical investigation of a marine alga-derived endophytic fungus, Acremonium vitellinum, resulted in the isolation of three chloramphenicol derivatives (compounds 1–3). Their chemical structures were elucidated by detailed analysis of their nuclear magnetic resonance spectra, high-resolution electrospray ionization mass spectrometry, and by comparison with the data available in the literature. In this paper, compound 2 was firstly reported as the natural origin of these fungal secondary metabolites. The insecticidal activities of compounds 1–3 against the cotton bollworm, Helicoverpa armigera, were evaluated. The natural compound 2 presented considerable activity against H. armigera, with an LC50 value of 0.56 ± 0.03 mg/mL (compared to matrine with an LC50 value of 0.24 ± 0.01 mg/mL). Transcriptome sequencing was used to evaluate the molecular mechanism of the insecticidal activities. The results presented in this study should be useful for developing compound 2 as a novel, ecofriendly and safe biopesticide.

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Section: Resultsmentioning

confidence: 99%

Insecticidal Activities of Chloramphenicol Derivatives Isolated from a Marine Alga-Derived Endophytic Fungus, Acremonium vitellinum, against the Cotton Bollworm, Helicoverpa armigera (Hübner) (Lepidoptera: Noctuidae)

et al. 2018

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“…The synthesis of the antibiotic chloramphenicol 17 is an attractive application of this methodology. Xu et al 18 have recently developed a rapid access in two steps to the natural syn diastereomer from amino acid 19. The direct and efficient synthesis of the anti-chloramphenicol from commercial diethylaminomalonate 24 is described in Scheme 6.…”

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confidence: 99%

Direct Synthesis of β-Hydroxy-α-amino AcidsviaDiastereoselective Decarboxylative Aldol Reaction

2013

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A straightforward metal-free synthesis of anti-β-hydroxy-α-amino acids is described. The organic base-mediated decarboxylative aldol reaction of cheap, readily available α-amidohemimalonates with various aldehydes afforded under very mild conditions anti-β-hydroxy-α-amido esters in high yields and complete diastereoselectivity. Simple one-pot subsequent transformations enabled the corresponding anti-β-hydroxy-α-amino acids or in a few examples their syn diastereomers to be obtained directly using epimerization conditions.

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“…Through conditional optimization, l - threo -MSPS was obtained with 94.6% de catalyzed by PsLTTA (Figure B, entry 3). , In general, l - threo -MSPS could be biosynthesized with good stereoselectivity using LTA or LTTA. To eventually be converted to florfenicol, l - threo -MSPS needs to be converted first to (1 R ,2 R )- p -methylsulfonyl phenylserinol ( 3a ), which requests two chemical steps comprising esterification and reduction . In order to establish a simplified synthetic route of florfenicol, we attempted to achieve the biobased production of 3a .…”

Section: Introductionmentioning

confidence: 99%

“…To eventually be converted to florfenicol, L-threo-MSPS needs to be converted first to (1R,2R)-p-methylsulfonyl phenylserinol (3a), which requests two chemical steps comprising esterification and reduction. 27 In order to establish a simplified synthetic route of florfenicol, we attempted to achieve the biobased production of 3a.…”

Section: ■ Introductionmentioning

confidence: 99%

One-Pot Asymmetric Synthesis of an Aminodiol Intermediate of Florfenicol Using Engineered Transketolase and Transaminase

et al. 2021

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Florfenicol is the 3′-fluoro derivative of thiamphenicol and has been widely used in veterinary medicine for its high antibacterial activity and safety. However, the development of simplified and environmentally friendly catalytic methods for the stereoselective production of florfenicol is a key challenge. Herein, we established a highly stereoselective enzymatic one-pot reaction for the synthesis of an aminodiol intermediate of florfenicol bearing two stereocenters from industrial raw material 4-(methylsulfonyl) benzaldehyde by coupling transketolase (TK) and ω-transaminase (TA). The enantioselectivity of TK from E. coli was converted from (S) (93% ee) to (R) (95% ee), and we also inverted the enantiopreference (E(S) = 9 to E(R) = 12) and ketone/ aldehyde substrate selectivity of TA ATA117 via structure-guided enzyme engineering. Docking calculations and molecular dynamics simulations of the wild-type and mutant enzymes unveiled the molecular basis for enzymatic stereocontrol. Using the engineered TK and TA, (1R,2R)-p-methylsulfonyl phenylserinol was biosynthesized with good yield (76%) and high stereoselectivity (96% de and >99% ee). Our work established an enzymatic synthetic route to (1R,2R)-p-methylsulfonyl phenylserinol, facilitating the development of a chemoenzymatic method for producing florfenicol.

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Stereoselective Synthesis of (−)‐Chloramphenicol, (+)‐Thiamphenicol and (+)‐Sphinganine via Chiral Tricyclic Iminolactone

Cited by 13 publications

References 31 publications

Insecticidal Activities of Chloramphenicol Derivatives Isolated from a Marine Alga-Derived Endophytic Fungus, Acremonium vitellinum, against the Cotton Bollworm, Helicoverpa armigera (Hübner) (Lepidoptera: Noctuidae)

Insecticidal Activities of Chloramphenicol Derivatives Isolated from a Marine Alga-Derived Endophytic Fungus, Acremonium vitellinum, against the Cotton Bollworm, Helicoverpa armigera (Hübner) (Lepidoptera: Noctuidae)

Direct Synthesis of β-Hydroxy-α-amino AcidsviaDiastereoselective Decarboxylative Aldol Reaction

One-Pot Asymmetric Synthesis of an Aminodiol Intermediate of Florfenicol Using Engineered Transketolase and Transaminase

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