Synthesis of the Spiroiminal Moiety of Marineosins A and B

Overview

Journal Org Lett

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2010 Mar 12

PMID 20218641

Citations 8

Authors

Xiao-Chuan Cai

Xiaoxing Wu

Barry B Snider

Affiliations

Soon will be listed here.

Abstract

A model for the spiroiminal moiety of marineosins A and B was prepared starting from methylvalerolactone. Addition of vinylmagnesium bromide, protection of the alcohol, and reaction of the vinyl ketone with a protected pyrrole-2-carbonitrile N-oxide gave an isoxazoline. Hydrogenolysis of the N-O bond with Raney nickel gave a keto imine that cyclized to a hemi-iminal. O-Methylation, acid-catalyzed cleavage of the TES group and spiroiminal formation, and deprotection completed a seven-step synthesis.

Citing Articles

Marine Pyrrole Alkaloids.

Seipp K, Geske L, Opatz T Mar Drugs. 2021; 19(9).

PMID: 34564176 PMC: 8471394. DOI: 10.3390/md19090514.

MarH, a Bifunctional Enzyme Involved in the Condensation and Hydroxylation Steps of the Marineosin Biosynthetic Pathway.

Lu W, Kancharla P, Reynolds K Org Lett. 2017; 19(6):1298-1301.

PMID: 28271893 PMC: 8168799. DOI: 10.1021/acs.orglett.7b00093.

Structure, Chemical Synthesis, and Biosynthesis of Prodiginine Natural Products.

Hu D, Withall D, Challis G, Thomson R Chem Rev. 2016; 116(14):7818-53.

PMID: 27314508 PMC: 5555159. DOI: 10.1021/acs.chemrev.6b00024.

Stereospecific synthesis of 23-hydroxyundecylprodiginines and analogues and conversion to antimalarial premarineosins via a Rieske oxygenase catalyzed bicyclization.

Kancharla P, Lu W, Salem S, Kelly J, Reynolds K J Org Chem. 2014; 79(23):11674-89.

PMID: 25380131 PMC: 4260665. DOI: 10.1021/jo5023553.

Elucidation of final steps of the marineosins biosynthetic pathway through identification and characterization of the corresponding gene cluster.

Salem S, Kancharla P, Florova G, Gupta S, Lu W, Reynolds K J Am Chem Soc. 2014; 136(12):4565-74.

PMID: 24575817 PMC: 3985843. DOI: 10.1021/ja411544w.

References

Cerdeno A, Bibb M, Challis G . Analysis of the prodiginine biosynthesis gene cluster of Streptomyces coelicolor A3(2): new mechanisms for chain initiation and termination in modular multienzymes. Chem Biol. 2001; 8(8):817-29. DOI: 10.1016/s1074-5521(01)00054-0. View

Furstner A . Chemistry and biology of roseophilin and the prodigiosin alkaloids: a survey of the last 2500 years. Angew Chem Int Ed Engl. 2003; 42(31):3582-603. DOI: 10.1002/anie.200300582. View

Williamson N, Fineran P, Leeper F, Salmond G . The biosynthesis and regulation of bacterial prodiginines. Nat Rev Microbiol. 2006; 4(12):887-99. DOI: 10.1038/nrmicro1531. View

Aldrich L, Dawson E, Lindsley C . Evaluation of the biosynthetic proposal for the synthesis of marineosins A and B. Org Lett. 2010; 12(5):1048-51. DOI: 10.1021/ol100034p. View

Mo S, Sydor P, Corre C, Alhamadsheh M, Stanley A, Haynes S . Elucidation of the Streptomyces coelicolor pathway to 2-undecylpyrrole, a key intermediate in undecylprodiginine and streptorubin B biosynthesis. Chem Biol. 2008; 15(2):137-48. DOI: 10.1016/j.chembiol.2007.11.015. View