Four novel gelsedine-type oxindole alkaloids from Gelsemium elegans

Four new gelsedine-type oxindole alkaloids (1-4) were isolated from the leaves and branches of Gelsemium elegans, together with 10 known alkaloids. The structures of the new alkaloids were determined by spectroscopic analyses and partial synthesis from known compounds. Gelsecrotonidine (1), 14-hydroxygelsecrotonidine (2), and 11-methoxygelsecrotonidine (3) possess an additional C₂ unit with an acetic acid residue compared to gelsenicine-related monoterpenoid indole alkaloids. 14-Hydroxygelsedilam (4) is an 18,19-nor-type monoterpenoid indole alkaloid.     

New oxindole and indole alkaloids from Gelsemium rankinii

Six new humantenine-type (1-6) and two new gelsemine-type (7, 8) oxindole alkaloids and one new indole alkaloid (9) were isolated from the leaves and branches of Gelsemium rankinii. The structures of the new alkaloids were determined by spectroscopic analyses. Among them, 6-hydroxyhumantenine (5) is the first example of a Gelsemium alkaloid with an oxygen function at C-6 position, and is a plausible biogenetic precursor of gelsemine-type alkaloids.     

The alkaloids of the mersinine group: a new subclass of the monoterpenoid indole alkaloids from Kopsia

A total of 16 alkaloids, exemplified by mersinine A and its congeners, and constituting a new subclass of the monoterpenoid indoles, were isolated exclusively and for the first time from Kopsia singapurensis. The structures of these alkaloids were established by spectroscopic methods and in some instances confirmed by X-ray diffraction analysis. A possible biogenetic route from an aspidofractinine precursor is proposed. Compounds 1, 2, 3, 9, and 10 were found to reverse multidrug-resistance in drug-resistant KB cells.     

Structures of new alkaloids sessilifoliamides A-D from Stemona sessilifolia

Four new Stemona alkaloids, sessilifoliamides A-D (1-4), were isolated from the roots of Stemona sessilifolia, along with five known alkaloids, stenine (5), 2-oxostenine (6), stemoninoamide (7), tuberostemonone (8), and neotuberostemonol (9). The structures and absolute configurations of the new alkaloids were determined by the spectral studies (HRMS, IR, ¹H, ¹³C, and 2D NMR), single-crystal X-ray analyses, and chemical correlations. The absolute configuration of 7 was also determined by the modified Mosher's method.     

An unexpected rearrangement of the benzofurobenzazepine skeleton of galanthamine-type alkaloids

Attempted cyclisation of N-methylated spiro benzazepine-cyclohexenone (5) into the corresponding N-methyl tetracyclic unit of galanthamine-type alkaloids (6) instead gave an unexpected rearrangement to yield a cyclopentanoisoquinolinone derivative (7). Methylation of the tetrahydrobenzofurobenzazepine tetracycle resulted in the expected N-methyl derivative 6, and the anomalous product 8, with structure similar to that of 7.     

The structures of three new Galbulimima alkaloids

The structures of three new alkaloids isolated from the bark of the rain forest tree Galbulimima belgraveana, have been determined by a combination of NMR spectroscopy and X-ray crystallography. One of the alkaloids, himgrine (5), was shown to be an oxygenated derivative of himbacine (1), while the second, GB16, (8) proved to be identical with a degradation product from himgaline (4). The remaining alkaloid, GB17 (12) possesses an entirely new and unexpected skeleton.     

Daphnezomines P, Q, R and S, new alkaloids from Daphniphyllum humile

Four new alkaloids, daphnezomines P-S (1-4), have been isolated from the fruits of Daphniphyllum humile, and the structures and the stereochemistry were elucidated on the basis of spectroscopic data including 2D NMR and MS/MS spectra, and chemical correlations. Daphnezomines P (1) and Q (2) were the first Daphniphyllum alkaloids with an iridoid glycoside moiety.     

Enantioselective electrophilic fluorination: a study of the fluorine-transfer from achiral N-F reagents to cinchona alkaloids

A transfer fluorination on cinchona alkaloids with the aid of achiral N-F fluorine-transfer reagents is described. Ten commercially available reagents were evaluated. Selectfluors™ 9 and 10, Accufluor™ 11, N-fluorobenzenesulfonimide (NFSi) 13, and N-fluoro-2,6-dichloropyridinium tetrafluoroborate 17 are effective fluorine-transfer reagents. The N-fluoroammonium salts of cinchona alkaloids thus prepared were employed in the construction of stereogenic fluorinated carbon centers with enantioselectivity as high as 85%. We also demonstrated that ionic liquids are effective “green” solvents for the development of this methodology.     

Oryzamutaic acids H-J, new alkaloids from an Oryza sativa mutant with yellow endosperm

Three new nitrogen-containing heterocyclic alkaloids, oryzamutaic acids H-J (1-3), were isolated from the endosperm (polished rice) of an Oryza sativa mutant. The structures and relative stereochemistries of 1-3 were elucidated on the basis of spectroscopic analyses. The presence of three carbons, each bound to a carboxyl group and a nitrogen atom in the structure of 1, suggests that oryzamutaic acids H-J (1-3) are generated from three molecules of a single amino acid.     

Lycopladines F and G, new C16N2-type alkaloids with an additional C4N unit from Lycopodium complanatum

Two new Lycopodium alkaloids, lycopladines F (1) and G (2), have been isolated from the club moss Lycopodium complanatum, and the structures and relative stereochemistries of 1 and 2 were elucidated on the basis of spectroscopic data. Lycopladine F (1) is a rare C₁₆N₂-type Lycopodium alkaloid possessing an amino acid residue (C₄N).     

Seven new alkaloids from the roots of Stemona tuberosa

Seven new alkaloids, named as 1,9-epoxy-9a-hydroxystenine (1), tuberostemoline A (2), tuberostemoline B (3), tuberostemoninol C (4), oxotuberostemonine A (5), the mixture of bisdehydrotuberostemonine D (6), and bisdehydrotuberostemonine E (7), together with four known alkaloids neotuberostemonine (8), sessilifoline B (9), stemoxazolidinone F (10), and tuberostemoninol A (11), were isolated from the roots of Stemona tuberosa. The structures of 1–7 were elucidated through extensive spectroscopic analysis, and the relative configurations of 1–6 and 8 were further confirmed by X-ray crystallographic data. Compounds 8, 9 and the mixture of 6 & 7 exhibited potential acetylcholinesterase (AChE) inhibitory activities.     

Daphniglaucins D-H, J, and K, new alkaloids from Daphniphyllum glaucescens

Five new fused-hexacyclic alkaloids, daphniglaucins D (1), E (2), F (3), G (4), and H (5), and two new yuzurimine-type alkaloids, daphniglaucins J (6) and K (7), have been isolated from the leaves of Daphniphyllum glaucescens, and the structures and relative stereochemistry were elucidated on the basis of spectroscopic data and chemical means.     

Seven new prenylated indole diketopiperazine alkaloids from holothurian-derived fungus Aspergillus fumigatus

Seven new prenylated indole diketopiperazine alkaloids, including compound 1, 3 spirotryprostatins C-E (2-4), 2 derivatives of fumitremorgin B (5 and 6), and 13-oxoverruculogen (7), have been isolated from the holothurian-derived fungus Aspergillus fumigatus, along with 12 known ones (8-19). The structures of the new compounds were determined on the basis of extensive spectroscopic data and amino acid analysis. All new compounds were evaluated for their cytotoxic activities on MOLT-4, A549, HL-60, and BEL-7420 cell lines by the MTT and SRB methods.     

New phlegmarane-type, cernuane-type, and quinolizidine alkaloids from two species of Lycopodium

Two new phlegmarane-type alkaloids, cermizines A (1) and B (2), three new quinolizidine alkaloids, cermizine C (3) and senepodines G (4) and H (5), and a new C₁₆N₂ type alkaloid consisting of a quinolizidine and a piperidine ring, cermizine D (6), as well as two new cernuane-type alkaloids, cernuine N-oxide (7) and lycocernuine N-oxide (8), have been isolated together with cernuine (9) and lycocernuine (10) from the club moss Lycopodium cernuum and L. chinense. The relative stereochemistry of 1-4 and 6, and the absolute stereochemistry of 5, 7, and 8 were elucidated by combination of NOESY correlations, modified Mosher's method, chemical transformations, and computational methods. Cermizine D (6) might be a biosynthetic intermediate of cernuane-type alkaloids such as 7-10.     

Agelasines O-U, new diterpene alkaloids with a 9-N-methyladenine unit from a marine sponge Agelas sp.

New diterpene alkaloids, agelasines O-U (1-7), have been isolated from an Okinawan marine sponge Agelas sp. The gloss structures and relative stereochemistries of 1-7 were elucidated from the spectroscopic data. Agelasines O-R (1-4) were the third examples of diterpene alkaloid with a 9-N-methyladenine and a pyrrole units. Agelasine O (1) has a halimane skeleton, while agelasines P-R (2-4) have a clerodane skeleton. Agelasines S-U (5-7) were new diterpene alkaloids with a 9-N-methyladenine unit consisting of a halimane skeleton, a labdane skeleton, and a clerodane skeleton, respectively. Agelasines O-R (1-4) and T (6) showed antimicrobial activities against several bacteria and fungi.     

Spironaamidine, a new spiroquinone-containing alkaloid from the marine sponge Leucetta microraphis

Spironaamidine (1), a unique spiroquinone-containing alkaloid, was isolated from the marine sponge, Leucetta microraphis, along with two known imidazole alkaloids, naamidine H (2) and (9E)-clathridine 9-N-(2-sulfoethyl)imine (3). Spironaamidine (1) showed antimicrobial activity against Bacillus cereus.     

Lyconadins C and F, new Lycopodium alkaloids from Lycopodium complanatum

New Lycopodium alkaloids, lyconadins C (1) and F (2), were isolated from the club moss Lycopodium complanatum. Lyconadin C (1) is a new C₁₆N₂-type Lycopodium alkaloid possessing unique fused-tetracyclic ring system consisting of a cycloheptene ring fused to a decahydroquinoline and pyridone rings. Lyconadin F (2) possesses a primary amide moiety in its molecular, which is the first example of Lycopodium alkaloids. Biogenetically, lyconadins C (1) and F (2) might be related to lyconadins A (4) and B (5). The structures and relative stereochemistry of 1 and 2 were elucidated on the basis of spectroscopic data. The absolute stereochemistry of 2 was elucidated by chemical correlations with lyconadin B (5) through hemiaminal form of lyconadin F (3).     

Hyrtimomines,indole alkaloids from Okinawan marine sponges Hyrtios spp.

Six new indole alkaloids, hyrtimomines F–K (1–6), were isolated from Okinawan marine sponges Hyrtios spp. The structures of 1–6 were elucidated on the basis of spectroscopic analysis. Hyrtimomine F (1) is a structurally unique bisindole alkaloid possessing an α-keto-?-caprolactam ring, while hyrtimomine G (2) is a symmetrical bisindole alkaloid. Hyrtimomines H–K (3–6) are indole alkaloids possessing β-carboline skeleton with an imidazolium unit. Antimicrobial activities of hyrtimomines F–K (1–6) were evaluated.     

Three new sulfur-containing alkaloids, polycarpaurines A, B, and C, from an Indonesian ascidian Polycarpa aurata

Three new sulfur-containing alkaloids, polycarpaurines A (1), B (2), and C (3) were isolated from the tropical ascidian Polycarpa aurata collected in Indonesia, together with six known compounds (4-9). The structures of new compounds were assigned on the basis of their spectral data. Compounds 1, 3, 4, and 8 inhibited colony formation of Chinese hamster V79 cells with EC₅₀ values of 6.8, 8.6, 3.8, and 10 μM, respectively. Compounds 2 and 7 showed modest activity against V79 cells (EC₅₀>10 μM).     

Complanadine B, obscurumines A and B, new alkaloids from two species of Lycopodium

A new dimer of C₁₆N₂ type alkaloid, complanadine B (1), and two new C₁₆N type alkaloids, obscurumines A (2) and B (3), have been isolated from the club moss Lycopodium complanatum and L. obscurum, respectively. The structures and stereochemistry of 1-3 were elucidated by combination of 2D NMR spectra and chemical transformation. Complanadine A (4) isolated together with 1 induced secretion of neurotrophic factors from human astrocytoma cells.