Total Syntheses of the Structures Assigned to Denigrins A, B, C, F, and G, 3,4-Diaryl-Pyrrole and -Pyrrolidinone Alkaloids, and the Conversion of Congener B into the Co-metabolite Spirodactylone.

The title marine natural products have been prepared by total synthesis and in the case of congeners 3, 6, and 7 for the first time. Each of these was obtained by manipulation of readily prepared denigrin B (2). The structure, 3, assigned to denigrin C is shown to be incorrect. Reaction of compound 2 with DDQ has led, in high yield, to the related natural product spirodactylone (16), while treating the corresponding permethyl ether 15 with PIFA/BF3·Et2O provides compound 20, embodying an isomeric framework.

Effect of Variations in the Fatty Acid Residue of Lactose Monoesters on Their Emulsifying Properties and Biological Activities.

Lactose fatty acid esters are high-value-added derivatives of lactose and represent a class of biodegradable, non-ionic, low-molecular-weight surfactants (emulsifiers) that have considerable potential in the food, cosmetic, and pharmaceutical industries. Certain lactose esters have also garnered attention for their biological activities. In this work, we detail syntheses of a homologous series of 6'- O-acyllactose esters of varying alkyl chain length (from 6 to 18 carbons) and report on their activities as surfactants as well as their antimicrobial and cytotoxic properties. The structure-property profiles established in this work revealed that while the medium-chain esters displayed excellent emulsifying properties and moderate antimicrobial activities, their longer chain congeners exhibited the highest cytotoxicities. As such, we have established that certain 6'- O-acyllactose esters are superior to their sucrose-derived and commercially exploited counterparts. These results will serve as a useful guide for the development of lactose esters as, inter alia, emulsifiers in the food industry.

Enzymatic Preparation of a Homologous Series of Long-Chain 6- O-Acylglucose Esters and Their Evaluation as Emulsifiers.

Sugar fatty acid esters are nonionic surfactants that are widely exploited in the food and cosmetics industries, as well as in the oral care and medical supply fields. Accordingly, new methods for their selective synthesis and the "tuning" of their emulsifying properties are of considerable interest. Herein we report simple and irreversible enzymatic esterifications of d-glucose with seven fatty acid vinyl esters. The foaming and emulsifying effects of the resulting 6- O-acylglucose esters were then evaluated. In accord with expectations, when the length of the alkyl side chain associated with the 6- O-acylglucose esters increases, then their hydrophilic-lipophilic balance (HLB) values decrease, while the stabilities of the derived emulsions improve. In order to maintain good foaming properties, alkyl side chains of at least 9 to 11 carbons in length are required. In the first such assays on 6- O-acylglucose esters, most of those described herein are shown to be nontoxic to the HepG2, MCF-7, LNacp, SW549, and LO-2 cell lines.