Hernandiaceae alkaloids

The noraporphine nandigerine, C18H17O4N, was isolated from Hernandia ovigera L. (Hernandiaceae). The base crystallized from methanol either as solvent free needles (mp 176°-177° [ajp - -248° in ethanol), or as plates of the methanol solvate, C]8Hi704N-CH30H (mp 99°-100°). The alkaloid hydrochloride salt melted at 245°-247° (decomp.) (33b). 

Isoquinolone alkaloids are a group of naturally occurring alkaloids mainly isolated from Hernandiaceae and Ranunculaceae. They can be subdivided into two categories those with a totally aromatic nucleus, such as 6,7-dimethoxy-2-methylisocar-bostyril (43 a) [25] and doryanine (43b) [26], and those with a C3-C4 single bond, includingN-methylcorydaldine (45a) and oxyhydrastinine (45b) (Scheme 11) [27]. 

The plants of Hernandiaceae comprise about sixty-five species in four generic kinds. The plants of Hernandia ovigera L. are widespread in the tropics and the subtropics. In Japan, these plants grow on the beaches of Okinawa and Ogasawara islands. In the Okinawa region, the plants have been used as therapeutic agents. A number of groups have been involved in the isolation and structure elucidation of aporphine-type and isoquinoline-type alkaloids from these plant materials as well... 

New sources for known alkaloids are (+ )-reticuline, Litsea xylanica (Laura-ceae) and Hernandia jamaicensis (Hernandiaceae) (see ref. 87) coclaurine, Sarcopetalum harveyanum Muell. (Menispermaceae) (— )-armepavine, Euony-mus europaeus (Celastraceae) (+ )-armepavine N-metho-salt, Xanthoxylum inerme Koidz. (Fagara boninensis Koidz.) (Rutaceae). ... 

Alkaloid from stem bark of Hernandia voyronii (Hernandiaceae). Cryst. (hexane). Mp 85-86°. [a] ... 

ALKALOIDS OF THE HERNANDIACEAE OCCURRENCE AND A COMPILATION OF THEIR BIOLOGICAL ACTIVITIES... 

Biological Activity of the Alkaloids found in the Hernandiaceae Species. 

Chart I. Basic skeleta of the alkaloids isolated from the Hernandiaceae, locator code, total number by skeleton type, and distribution in the genus. 

In the Hernandiaceae, only one benzylisoquinoline-phenanthrene alkaloid [( + )-hebridamine (VII.l)] was isolated from H. peltata Meissn. (46,47). This structural type is probably derived biogenetically from the oxidative coupling of two units of reticuline (II.8). 

Isoquinoline alkaloids are formed by the reaction of phenylethylamine and formaldehyde, followed by cyclization (28). Menachery has reviewed the occurrence and properties of this structural type of alkaloids (49). In the Hernandiaceae, only five such alkaloids (XI.1-XI.4 and XII.l) have so far shown restricted occurrence in a few species of Hernandia (Table I). Among them, A-methylcorydaldine (XI.l) showed cytotoxic activity in vitro against P-388, CA-KB-16, CA-A549 cells, and the human colon cancer cell line HT-29 (25) and northalifoline (XI.3) exhibited weak in vitro cytotoxity against CA-A549 cells (26) (Table II). 

A few alkaloids with pyridine (XIII), proaporphine (XIV), and phenanthrene (XVI) nuclei were also found in the Hernandia, Gyrocarpus, and Illigera species, respectively (Table I). Phenanthrene alkaloids, also known as seco-aporphines, are a very rare type, probably formed biogenetically from an aporphine precursor through the opening of ring B (28). Castedo and Tojo have reviewed their chemistry (50). From the family Hernandiaceae only thaliporphinemethine (XVI.l) was isolated from I. pentaphylla Welw. (51). 

The present work is a review of articles published in the literature (275 references) regarding alkaloids isolated from plants of the family Hernandiaceae and their biological activity. The chemistry of this family has been reviewed previously, but since the last review (published in 1971) (27), new species have been chemically investigated and several different structural types of alkaloids have been isolated. 

List of the Alkaloids Isolated from Hernandiaceae Species... 

This volume of The Alkaloids Chemistry and Biology might be called The Brazilian Volume since each of the three chapters is compiled and written exclusively by Brazilian authors. This is definitely a reflection of the tremendous current Brazilian interest in the investigation and potentiation of their vast array of natural resources, and particularly of alkaloid-bearing plants. In this volume, the recent progress relating to three groups of alkaloids, the protoberberine alkaloids, the Stemona alkaloids, and the alkaloids of the plant family Hernandiaceae is reviewed. 

Finally, in the third chapter, Conserva, Pereira, and Barbosa-Filho review the numerous alkaloids derived from the plant family Hernandiaceae. Their isolation, structural diversity, and substantial range of biological effects are described and well cataloged. 

ReticuIine has been found in many plants of the families of Annonaceae, Hernandiaceae, Lauraceae, Monimiaceae, Papveraceae, and others. This alkaloid is known to serve as an important intermediate in the biosynthesis of more complicated isoquinoline alkaloids. 

Alkaloids having the same fundamental skeleton as magnoflorine are called aporphine-type alkaloids (58, 140). This class of alkaloids is widely distributed in nature. At least 18 families are known to contain aporphine-type alkaloids. Some of them are Annonaceae, Magnoliaceae, Lauraceae, and Hernandiaceae (Magnoliales), Ranunculaceae, Berberidaceae, and Menispermaceae (Ranun-culales), Aristrochiaceae (Aristrochiales), Papaveraceae (Fumariaceae) (Papavera-les), Rutaceae (Rutales), and Rhamnaceae (Rhamnales). 

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