Halisphingosines A and B, Modified Sphingoid Bases from Haliclona tubifera. Assignment of Configuration by Circular Dichroism and van’t Hoff’s Principle of Optical Superposition

Abstract

Halisphingosines A (1) and B (2), modified long-chain sphingoid bases, from the marine sponge Haliclona tubifera collected in Brazil, were characterized after conversion to their N-Boc derivatives. The 2R,3R,6R configuration of halisphingosine A, a compound first reported from Haliclona sp. South Korea, was confirmed using a novel CD approach: deconvolution of exciton coupling from mono- and tri-naphthoyl derivatives obtained by derivatization of the natural product. The sensitive CD deconvolution method, applicable to sub-milligram samples, simultaneously predicted the relative and absolute configuration of three stereocenters in halisphingosine A with precision and accuracy. Halisphingosine B was assigned by correlation to halisphingosine A.

Sphingosines Derived from Marine Sponge as Potential Multi-Target Drug Related to Disorders in Cancer Development

“…The first one, about biological properties in crude extracts [ 13 ]. Recently, we have reported the isolation of two modified long-chain sphingoid bases, named Halisphingosines A and B ( Figure 1 ), and the absolute configuration of these compounds was also assigned [ 14 ].…”

“… Sphingoid bases isolated from EtOAc fraction of H. tubifera : (2 R ,3 R ,6 R ,7 Z )-2-aminooctadec-7-ene-1,3,6-triol ( 1 ); and (2 R ,3 R ,6 R )-2-aminooctadec-1,3,6-triol ( 2 ) [ 14 ]. …”

Antibiotic activity and microbial community of the temperate sponge, Haliclona sp.

“…), sphingoid bases (Molinski et al . ), steroids and terpenoids (Sakowicz et al . ; Blackburn and Faulkner ; Volk and Kock ; Volk et al .…”

“…This selective pressure is thought to drive the evolution of natural products with potent bioactivity that may be exploited for pharmaceutical development (Laport et al 2009;Sepcic et al 2010). Sponges in the genus Haliclona are a particularly rich source of natural products, including amino alcohols (Devijver et al 2000), macrocyclic diamides (Jang et al 2009), sphingoid bases (Molinski et al 2013), steroids and terpenoids (Sakowicz et al 1998;Blackburn and Faulkner 2000;Volk and Kock 2003;Volk et al 2004;Yu et al 2006;Trianto et al 2011), alkaloids (Charan et al 1996;Clark et al 1998;Schmidt et al 2011Schmidt et al , 2012Kock et al 2013), hydroquinones (Bokesch et al 2002), acetylenes (Chill et al 2000;Nuzzo et al 2012), cyclic peptides (Randazzo et al 2001) and nucleosides (Wang et al 2009). When we began this study, we were interested in natural products from marine invertebrates in temperate habitats, as they are less studied than their tropical counterparts.…”

Natural Products from Marine Invertebrates and Microorganisms in Brazil between 2004 and 2017: Still the Challenges, More Rewards

“…55 The sponge Haliclona tubifera provided the known halisphingosine A (106, Figure 13) and the new halisphingosine B (107, Figure 13), long-chain sphingoid bases derivatives, which possess an uncommon L-threo configuration for this class of natural products. 56 Cyclic alkylpyridine oligomers ( Figure 13) haliotoxin (108) and amphitoxin (109) have been isolated from the marine sponge Amphimedon sp. and displayed antifungal activity against Aspergillus flavus, a storage contaminant fungus affecting for commercial agricultural products.…”