Synthesis of Cycloprodigiosin Identifies the Natural Isolate as a Scalemic Mixture

Johnson, Rebecca E.; de Rond, Tristan; Lindsay, Vincent N.  G.; Keasling, Jay D.; Sarpong, Richmond

doi:10.1021/acs.orglett.5b01527

Title: Synthesis of Cycloprodigiosin Identifies the Natural Isolate as a Scalemic Mixture

Journal Article · Fri Jul 17 00:00:00 EDT 2015 · Organic Letters

DOI:https://doi.org/10.1021/acs.orglett.5b01527· OSTI ID:1257348

Johnson, Rebecca E.; de Rond, Tristan; Lindsay, Vincent N. G.; Keasling, Jay D.; Sarpong, Richmond

We prepared the enantiomers of the natural product cycloprodigiosin using an expedient five-step synthetic sequence that takes advantage of a Schöllkopf–Barton–Zard (SBZ) pyrrole annulation with a chiral isocyanoacetate and a nitrocyclohexene derivative. Using chiral HPLC and X-ray crystallographic analyses of the synthetically prepared material and natural isolate (isolated from the marine bacterium Pseudoalteromonas rubra), naturally occurring cycloprodigiosin was determined to be a scalemic mixture occurring in an enantiomeric ratio of 83:17 (R)/(S) at C4'.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-05CH11231; S10-RR027172; 1341894

OSTI ID:: 1257348

Journal Information:: Organic Letters, Vol. 17, Issue 14; ISSN 1523-7060

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 12 works

Citation information provided by
Web of Science

References (28)

Cycloprodigiosin hydrochloride, a new H+/Cl? symporter, induces apoptosis in human and rat hepatocellular cancer cell linesin vitro and inhibits the growth of hepatocellular carcinoma xenografts in nude mice Yamamoto, Chizuko; Takemoto, Hiroto; Kuno, Kenji Hepatology, Vol. 30, Issue 4 https://doi.org/10.1002/hep.510300417	journal	October 1999
Induction of apoptosis of activated murine splenic T cells by cycloprodigiosin hydrochloride, a novel immunosuppressant Azuma, Takayoshi; Watanabe, Naoko; Yagisawa, Hitoshi Immunopharmacology, Vol. 46, Issue 1 https://doi.org/10.1016/S0162-3109(99)00153-8	journal	January 2000
Cycloprodigiosin Hydrochloride Obtained from Pseudoalteromonas denitrificans Is a Potent Antimalarial Agent. Kim, Hye-Sook; Hayashi, Mitsuko; Shibata, Yasuharu Biological and Pharmaceutical Bulletin, Vol. 22, Issue 5 https://doi.org/10.1248/bpb.22.532	journal	January 1999
Chemistry and Biology of Roseophilin and the Prodigiosin Alkaloids: A Survey of the Last 2500 Years Fürstner, Alois Angewandte Chemie International Edition, Vol. 42, Issue 31 https://doi.org/10.1002/anie.200300582	journal	August 2003
Prodigiosin alkaloids: recent advancements in total synthesis and their biological potential Nisha, Nisha; Kumar, Kewal; Kumar, Vipan RSC Advances, Vol. 5, Issue 15 https://doi.org/10.1039/C4RA10296G	journal	January 2015
The biosynthesis and regulation of bacterial prodiginines Williamson, Neil R.; Fineran, Peter C.; Leeper, Finian J. Nature Reviews Microbiology, Vol. 4, Issue 12 https://doi.org/10.1038/nrmicro1531	journal	December 2006
Influence of the A -Ring on the Proton Affinity and Anticancer Properties of the Prodigiosins Melvin, Matt S.; Tomlinson, John T.; Park, Gyungse Chemical Research in Toxicology, Vol. 15, Issue 5 https://doi.org/10.1021/tx025507x	journal	April 2002
Prodigiosins uncouple lysosomal vacuolar-type ATPase through promotion of H+/Cl− symport Ohkuma, Shoji; Sato, Tomohiko; Okamoto, Masayuki Biochemical Journal, Vol. 334, Issue 3 https://doi.org/10.1042/bj3340731	journal	September 1998
Prodigiosin is a chloride carrier that can function as an anion exchanger Seganish, Jennifer L.; Davis, Jeffery T. Chemical Communications, Issue 46 https://doi.org/10.1039/b511847f	journal	January 2005
Molecular Interactions of Prodiginines with the BH3 Domain of Anti-Apoptotic Bcl-2 Family Members Hosseini, Ali; Espona-Fiedler, Margarita; Soto-Cerrato, Vanessa PLoS ONE, Vol. 8, Issue 2 https://doi.org/10.1371/journal.pone.0057562	journal	February 2013
Elimination of Butylcycloheptylprodigiosin as a Known Natural Product Inspired by an Evolutionary Hypothesis for Cyclic Prodigiosin Biosynthesis Jones, Brian T.; Hu, Dennis X.; Savoie, Brett M. Journal of Natural Products, Vol. 76, Issue 10 https://doi.org/10.1021/np400531b	journal	September 2013
Small molecule obatoclax (GX15-070) antagonizes MCL-1 and overcomes MCL-1-mediated resistance to apoptosis Nguyen, M.; Marcellus, R. C.; Roulston, A. Proceedings of the National Academy of Sciences, Vol. 104, Issue 49 https://doi.org/10.1073/pnas.0709443104	journal	November 2007
Stereochemical Elucidation of Streptorubin B Haynes, Stuart W.; Sydor, Paulina K.; Corre, Christophe Journal of the American Chemical Society, Vol. 133, Issue 6 https://doi.org/10.1021/ja109164t	journal	February 2011
Regio- and stereodivergent antibiotic oxidative carbocyclizations catalysed by Rieske oxygenase-like enzymes Sydor, Paulina K.; Barry, Sarah M.; Odulate, Olanipekun M. Nature Chemistry, Vol. 3, Issue 5 https://doi.org/10.1038/nchem.1024	journal	April 2011
C–H activation is a Reiske business Bruner, Steven D. Nature Chemistry, Vol. 3, Issue 5 https://doi.org/10.1038/nchem.1038	journal	April 2011
The biosynthesis of metacycloprodigiosin and undecylprodigiosin Wasserman, H. H.; Shaw, C. K.; Sykes, R. J. Tetrahedron Letters, Vol. 15, Issue 33 https://doi.org/10.1016/S0040-4039(01)91743-5	journal	January 1974
Cycloprodigiosin from beneckea gazogenes Gerber, Nancy N. Tetrahedron Letters, Vol. 24, Issue 27 https://doi.org/10.1016/S0040-4039(00)88026-0	journal	January 1983
A revised structure for cycloprodigiosin Lattasch, Hartmut; Thomson, Ronald H. Tetrahedron Letters, Vol. 24, Issue 26 https://doi.org/10.1016/S0040-4039(00)87981-2	journal	January 1983
The synthesis of (±)-cycloprodigiosin Wasserman, Harry H.; Fukuyama, James M. Tetrahedron Letters, Vol. 25, Issue 13 https://doi.org/10.1016/S0040-4039(01)80165-9	journal	January 1984
Enantioselective Total Synthesis and Confirmation of the Absolute and Relative Stereochemistry of Streptorubin B Hu, Dennis X.; Clift, Michael D.; Lazarski, Kiel E. Journal of the American Chemical Society, Vol. 133, Issue 6 https://doi.org/10.1021/ja109165f	journal	February 2011
Application of In Situ-Generated Rh-Bound Trimethylenemethane Variants to the Synthesis of 3,4-Fused Pyrroles Schultz, Erica E.; Sarpong, Richmond Journal of the American Chemical Society, Vol. 135, Issue 12 https://doi.org/10.1021/ja401380d	journal	March 2013
A new synthesis of pyrroles from nitroalkenes Barton, Derek H. R.; Zard, Samir Z. Journal of the Chemical Society, Chemical Communications, Issue 16 https://doi.org/10.1039/c39850001098	journal	January 1985
A new synthesis of conjugated nitro cyclo olefins, unusually versatile synthetic intermediates Corey, E. J.; Estreicher, Herbert Journal of the American Chemical Society, Vol. 100, Issue 19 https://doi.org/10.1021/ja00487a088	journal	September 1978
C–H Methylation of Heteroarenes Inspired by Radical SAM Methyl Transferase Gui, Jinghan; Zhou, Qianghui; Pan, Chung-Mao Journal of the American Chemical Society, Vol. 136, Issue 13 https://doi.org/10.1021/ja5007838	journal	March 2014
Manganese(III) Complexes of Bis(hydroxyphenyl)dipyrromethenes Are Potent Orally Active Peroxynitrite Scavengers Rausaria, Smita; Kamadulski, Andrew; Rath, Nigam P. Journal of the American Chemical Society, Vol. 133, Issue 12 https://doi.org/10.1021/ja110427e	journal	March 2011
Two-step synthesis of the bipyrrole precursor of prodigiosins Dairi, Kenza; Tripathy, Sasmita; Attardo, Giorgio Tetrahedron Letters, Vol. 47, Issue 15 https://doi.org/10.1016/j.tetlet.2006.02.035	journal	April 2006
Facile synthesis of a chiral auxiliary bearing the isocyanide group Ilankumaran, Palanichamy; Kisanga, Philip; Verkade, John G. Heteroatom Chemistry, Vol. 12, Issue 7 https://doi.org/10.1002/hc.1086	journal	January 2001
Colour Change of Prodigiosin Hearn, Walter R.; Medina-Castro, Jorge; Elson, Michael K. Nature, Vol. 220, Issue 5163 https://doi.org/10.1038/220170a0	journal	October 1968

Cited By (4)

Preparation of Cyclic Prodiginines by Mutasynthesis in Pseudomonas putida KT2440 Klein, Andreas Sebastian; Brass, Hannah Ursula Clara; Klebl, David Paul ChemBioChem, Vol. 19, Issue 14 https://doi.org/10.1002/cbic.201800154	journal	May 2018
Synthesis of Highly Enantio-Enriched Heliespirones A and C by a Diastereoselective Aromatic Claisen Rearrangement Norcott, Philip; McErlean, Christopher S. P. Australian Journal of Chemistry, Vol. 71, Issue 5 https://doi.org/10.1071/ch18019	journal	January 2018
Culturing marine bacteria from the genusPseudoalteromonason a cotton scaffold alters secondary metabolite production Timmermans, Marshall L.; Picott, Katherine J.; Ucciferri, Lorena MicrobiologyOpen, Vol. 8, Issue 5 https://doi.org/10.1002/mbo3.724	journal	October 2018
Oxidative cyclization of prodigiosin by an alkylglycerol monooxygenase-like enzyme de Rond, Tristan; Stow, Parker; Eigl, Ian Nature Chemical Biology, Vol. 13, Issue 11 https://doi.org/10.1038/nchembio.2471	journal	September 2017

Figures / Tables (6)

Similar Records

Fluoranthene metabolism: Human and rat liver microsomes display different stereoselective formation of the trans-2,3-dihydrodiol

Journal Article · Sun Nov 01 00:00:00 EST 1992 · Chemical Research in Toxicology; (United States) · OSTI ID:1257348

Day, B W; Sahali, Y; Hutchins, D A; +7 more

Oxidative cyclization of prodigiosin by an alkylglycerol monooxygenase-like enzyme

Journal Article · Mon Sep 11 00:00:00 EDT 2017 · Nature Chemical Biology · OSTI ID:1257348

de Rond, Tristan; Stow, Parker; Eigl, Ian; +8 more

Congener specific determination and enantiomeric ratios of chiral polychlorinated biphenyls in striped dolphins (Stenella coeruleoalba) from the Mediterranean Sea

Journal Article · Tue Jun 01 00:00:00 EDT 1999 · Environmental Science and Technology · OSTI ID:1257348

Reich, S; Schurig, V; Jimenez, B; +3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY