Chiral Indolizinium Salts Derived from 2-Pyridinecarbaldehyde-First Diastereoselective Syntheses of (-)-1-epi-lentiginosine.

The first diastereoselective synthesis of (-)-1-epi-lentiginosine from a common chiral trans-epoxyamide derived from 2-pyridincarbaldehyde is reported. This methodology involves a sequential oxirane ring opening and intramolecular 5-exo-tet cyclization of tosylate trans-epoxyalcohol to afford a diastereomeric mixture of indolizinium salts in a one-pot fashion, followed by regio- and diastereospecific pyridinium ring reduction.

1 H and 13 C NMR data, occurrence, biosynthesis, and biological activity of Piper amides.

Alkamides are the major and characteristic chemical compounds of the plants belonging to the Piper genus. These compounds are responsible for the flavor of pepper spices and for its broad use in cuisine across many regions of the world. Humans are in contact every day with these substances, which additionally show a broad variety of pharmacological activities, making them an important research target. A large amount of NMR data for these natural products is dispersed throughout literature. Its organization will help those research groups interested in their identification and structural elucidation. This review summarizes the 1 H and 13 C NMR data of 268 Piper amides in a systematic and orderly way, with a discussion on their biological activities, biosynthetic aspects, and NMR analysis of typical and relevant aspects of this information.

(1) H and (13) C NMR data on natural and synthetic capsaicinoids.

Capsaicinoids are the compounds responsible for the pungency of chili peppers. These substances have attracted the attention of many research groups in recent decades because of their antinociceptive, analgesic, anti-inflammatory, and anti-obesity properties, among others. There are nearly 160 capsaicinoids reported in the literature. Approximately 25 of them are natural products, while the rest are synthetic or semi-synthetic products. A large amount of NMR data for the capsaicinoids is dispersed throughout literature. Therefore, there is a need to organize all this NMR data in a systematic and orderly way. This review summarizes the (1) H and (13) C NMR data on 159 natural and synthetic capsaicinoids, with a brief discussion of some typical and relevant aspects of these NMR data. Copyright © 2015 John Wiley & Sons, Ltd.

Chemical composition of Helietta parvifolia and its in vitro anticholinesterase activity.

The chemical composition of the essential oil and the n-hexane (Hex), Ethyl Acetate (EtOAc) and butanol (BuOH) extracts from the leaves of Helietta parvifolia were determined by detailed GC-MS analysis, spectroscopic and spectrometric data. Eighty-four compounds were identified, revealing a furoquinoline alkaloid-rich composition. The phytochemical analysis of the extracts allowed the isolation of eigth furoquinoline alkaloids. Retention indices in GC-MS for six of this alkaloids are reported for the first time. Furoquinoline alkaloids are acethylcholinesterase inhibitors. Thus, the essential oil and extracts were submitted to this in vitro assay. The EtOAc and BuOH extracts showed potent activity, with IC50 of 9.7 and 12.9 µg mL-1, respectively. Additionaly, a correlation of their chemical constituents, established by principal component analysis (PCA) demostrated a similar profile and a high content of alkaloids. It is for these reasons that we can assume that the alkaloid content in these extracts could be responsible for their anticholinesterase activity.

Accurate stereochemistry for two related 22,26-epiminocholestene derivatives.

Regioselective opening of ring E of solasodine under various conditions afforded (25R)-22,26-epiminocholesta-5,22(N)-diene-3beta,16beta-diyl diacetate (previously known as 3,16-diacetyl pseudosolasodine B), C(31)H(47)NO(4), or (22S,25R)-16beta-hydroxy-22,26-epiminocholesta-5-en-3beta-yl acetate (a derivative of the naturally occurring alkaloid oblonginine), C(29)H(47)NO(3). In both cases, the reactions are carried out with retention of chirality at the C16, C20 and C25 stereogenic centers, which are found to be S, S and R, respectively. Although pseudosolasodine was synthesized 50 years ago, these accurate assignments clarify some controversial points about the actual stereochemistry for these alkaloids. This is of particular importance in the case of oblonginine, since this compound is currently under consideration for the treatment of aphasia arising from apoplexy; the present study defines a diastereoisomerically pure compound for pharmacological studies.

Synthetic pathway to 22,23-dioxocholestanic chain derivatives and their usefulness for obtaining brassinosteroid analogues.

Recognizing the functionality of the pentacyclic steroidal derivative 7a as important synthon to obtain new brassinosteroid analogs, we have accomplished the derivatization of hecogenin, a sapogenin from the 25R serie containing a carbonyl group at C-12, to a 22,23-dioxocholestanic chain derivative. Starting from hecogenin acetate (5a) or hecogenin tosylate (5b), we obtained two pentacyclic derivatives (7a and 7b) which were subjected to an oxidation reaction on the double bond at C-12(23) to obtain a 22,23-dioxocholestanic chain, with the regeneration of the carbonyl group at C-12. Reduction of the carbonyl groups lead to the 20-epi-12,23-dihydroxy-22-oxo system 11a-b. The absolute configuration of compound 11a was established by X-ray diffraction analysis.

Rapid conversion of spirostans into furostan skeletons at room temperature.

We report a facile protocol to obtain 22-substituted furostans and pseudosapogenins in high yields from (25R)- and (25S)-sapogenins. This method involves the treatment of the sapogenin with acetic-trifluoroacetic mixed anhydride and BF(3)·OEt(2) at room temperature, followed by the addition of a nucleophile (H(2)O, MeOH or KSeCN). In the case of 22-hydroxyfurostans, they can be transformed to pseudosapogenins by treatment with p-toluensulfonic acid.