Studies Towards the -derived Alkaloids Spirocalcaridine A and B - Possible Biosynthetic Implications

Overview

Journal European J Org Chem

Specialty Biochemistry

Date 2015 Aug 11

PMID 26257576

Citations 1

Authors

Panduka B Koswatta

Jayanta Das

Muhammed Yousufuddin

Carl J Lovely

Affiliations

Soon will be listed here.

Abstract

An exploration of an abiotic approach to spirocalcaridines A and B is described centered on electrophile-induced dearomatizing spirocyclization of aryl enyne derivatives. Elaboration of the α-iodoenone via an Ullmann-like, copper-catalyzed amidation provided a formamide which upon treatment with methylamine undergoes a dienol-arene rearrangement, providing the corresponding kealiinine-like framework. This observation suggests a possible biosynthetic links between the spirocalcaridines and the naphthimidazole group of alkaloids.

Citing Articles

Investigation of Dearomatizing Spirocyclizations and Spirocycle Functionalization En Route to Spirocalcaridines A and B-Some Trials and Tribulations.

Singh R, Gout D, Mao J, Kroll P, Lovely C Molecules. 2025; 30(5).

PMID: 40076366 PMC: 11902021. DOI: 10.3390/molecules30051143.

Total synthesis and cytotoxicity of Leucetta alkaloids.

Koswatta P, Kasiri S, Das J, Bhan A, Lima H, Garcia-Barboza B Bioorg Med Chem. 2017; 25(5):1608-1621.

PMID: 28159485 PMC: 5596918. DOI: 10.1016/j.bmc.2017.01.024.

References

Lima H, Sivappa R, Yousufuddin M, Lovely C . Total synthesis of 7'-desmethylkealiiquinone. Org Lett. 2012; 14(9):2274-7. PMC: 3785306. DOI: 10.1021/ol300704w. View

Zhang X, Larock R . Synthesis of spiro[4.5]trienones by intramolecular ipso-halocyclization of 4-(p-methoxyaryl)-1-alkynes. J Am Chem Soc. 2005; 127(35):12230-1. DOI: 10.1021/ja053079m. View

Unsworth W, Cuthbertson J, Taylor R . Total synthesis of spirobacillene A. Org Lett. 2013; 15(13):3306-9. DOI: 10.1021/ol4013958. View

Hassan W, Edrada R, Ebel R, Wray V, Berg A, Van Soest R . New imidazole alkaloids from the Indonesian sponge Leucetta chagosensis. J Nat Prod. 2004; 67(5):817-22. DOI: 10.1021/np0305223. View

Zheng N, Buchwald S . Copper-catalyzed regiospecific synthesis of N-alkylbenzimidazoles. Org Lett. 2007; 9(23):4749-51. DOI: 10.1021/ol7020737. View

Sivappa R, Koswatta P, Lovely C . Oxidative reactions of tetrahydrobenzimidazole derivatives with N-sulfonyloxaziridines. Tetrahedron Lett. 2011; 48(33):5771-5775. PMC: 2794047. DOI: 10.1016/j.tetlet.2007.06.088. View

Das J, Bhan A, Mandal S, Lovely C . Total syntheses and cytotoxicity of kealiiquinone, 2-deoxy-2-aminokealiiquinone and analogs. Bioorg Med Chem Lett. 2013; 23(22):6183-7. PMC: 3876475. DOI: 10.1016/j.bmcl.2013.08.093. View

Zavesky B, Babij N, Wolfe J . Synthesis of substituted 2-aminoimidazoles via Pd-catalyzed alkyne carboamination reactions. Application to the synthesis of preclathridine natural products. Org Lett. 2014; 16(18):4952-5. PMC: 4168774. DOI: 10.1021/ol502471x. View

Focken T, Charette A . Stereoselective synthesis of pyridinones: application to the synthesis of (-)-barrenazines. Org Lett. 2006; 8(14):2985-8. DOI: 10.1021/ol0609006. View

10.

Tang B, Tang D, Tang S, Yu Q, Zhang Y, Liang Y . Selective synthesis of spiro[4,5]trienyl acetates via an intramolecular electrophilic ipso-iodocyclization process. Org Lett. 2008; 10(6):1063-6. DOI: 10.1021/ol703050z. View

11.

Lima H, Sivappa R, Yousufuddin M, Lovely C . Total synthesis of 7'-desmethylkealiiquinone, 4'-desmethoxykealiiquinone, and 2-deoxykealiiquinone. J Org Chem. 2014; 79(6):2481-90. PMC: 3986028. DOI: 10.1021/jo4027337. View

12.

Koswatta P, Sivappa R, Dias H, Lovely C . Total synthesis of (+/-)-calcaridine A and (+/-)-epi-calcaridine A. Org Lett. 2008; 10(21):5055-8. PMC: 2650485. DOI: 10.1021/ol802018r. View

13.

Gibbons J, Gligorich K, Welm B, Looper R . Synthesis of the reported structures for kealiinines B and C. Org Lett. 2012; 14(18):4734-7. PMC: 3619427. DOI: 10.1021/ol3019242. View

14.

Lima H, Garcia-Barboza B, Khatibi N, Lovely C . Total syntheses of isonaamine C and isonaamidine E. Tetrahedron Lett. 2011; 52(44):5725-5727. PMC: 3225899. DOI: 10.1016/j.tetlet.2011.08.030. View

15.

Roue M, Quevrain E, Domart-Coulon I, Bourguet-Kondracki M . Assessing calcareous sponges and their associated bacteria for the discovery of new bioactive natural products. Nat Prod Rep. 2012; 29(7):739-51. DOI: 10.1039/c2np20040f. View

16.

Zhang X, Sarkar S, Larock R . Synthesis of naphthalenes and 2-naphthols by the electrophilic cyclization of alkynes. J Org Chem. 2006; 71(1):236-43. PMC: 2532853. DOI: 10.1021/jo051948k. View

17.

Koswatta P, Lovely C . Structure and synthesis of 2-aminoimidazole alkaloids from Leucetta and Clathrina sponges. Nat Prod Rep. 2010; 28(3):511-28. DOI: 10.1039/c0np00001a. View

18.

Kotecki B, Fernando D, Haight A, Lukin K . A general method for the synthesis of unsymmetrically substituted ureas via palladium-catalyzed amidation. Org Lett. 2009; 11(4):947-50. DOI: 10.1021/ol802931m. View

19.

Edrada R, Stessman C, Crews P . Uniquely modified imidazole alkaloids from a calcareous Leucetta sponge. J Nat Prod. 2003; 66(7):939-42. DOI: 10.1021/np020503d. View

20.

Gupta M, Li Z, Snowden T . Preparation of one-carbon homologated amides from aldehydes or primary alcohols. Org Lett. 2014; 16(6):1602-5. DOI: 10.1021/ol500200n. View