Liverworts compounds from

Marchantia brachiata (Sw.) Schiffn. is a liverwort that also enjoys a wide distribution. It is included here to offset the idea that liverworts of wide occurrence need to exhibit different chemistries in order to attract attention. Nagashima et al. (1999) identified four compounds from plants collected in Ecuador 3,4-dimethoxystyrylbenzene [456], 2,4,5-trimethoxystyrylbenzene [457], P-caryophyllene [458], and bicycloger-macrene [459], In the words of those workers, there was ... ostensibly no metabolic differences between Marchantia brachiata collected in the Netherlands Antilles, Saba, and in Ecuador. ... 

Nagashima, F., Murakami, Y., and Asakawa, Y., Aromatic compounds from the Ecuadorian liverwort Marchesinia brachiata a revision, Phytochemistry, 51, 1101, 1999. 

Yoshida, T., Toyota, M., and Asakawa, Y. (1997). Scapaundulins A and B, two novel dimeric labdane diterpenoids, and related compounds from the Japanese liverwort Scapania undulata (L.) Dum. Tetrahedron Lett. 38, 1975-1978. 

Harinantenaina, L., D.N. Quang, T. Nishizawa et al., 2007. Bioactive compounds from liverworts Inhibition of lipopolysaccharide-induced inducible NOS mRNA in RAW 264.7 cells by herbertenoids and cuparenoids. Phvtomedicine. 14 486-491. 

Nagashima F, Kuba Y, Asakawa Y (2006) Diterpenoids and aromatic compounds from the three New Zealand liverworts Jamesoniella kirkii, Balantiopsis rosea, and Radula species. Chem Pharm Bull 54 902-906... 

Scher JM, Burgess EJ, Lorimerb SD, Perry NB (2002) A cytotoxic sesquiterpene and unprecedented sesquiterpene-bisbibenzyl compounds from the liverwort Schistochila glaucescens. Tetrahedron 58 7875-7882... 

Nagashima F, Momosaki S, Watanabe Y, Toyota M, Huneck S, Asakawa Y (1996) Terpenoids and aromatic compounds from six liverworts. Phytochemistry 41 207-211... 

One of the distinguishing features of liverworts is their capacity to produce a variety of volatile, often very fragrant, oils that occur in oil bodies distributed over much of the surface of the organism. Several of these volatile compounds figure prominently in defining geographically different chemotypes in several countries. Toyota et al. (1997) examined 280 specimens of C. conicum collected at Kamikatsu-cho and Katsuura-cho, both Katsuura-gun, Tokushima. Three chemotypes were identified based upon their major components. Chemotype-I-accumulated (-)-sabinene [420], chemotype-II-accumulated (H-)-bomyl acetate [421], and chemotype III was characterized by methyl cinnamate [422] (see Pig. 5.4 for structures). In addition to a number of compounds known from previous studies of C. conicum, three... 

Recent work identifying Plagiochila retrorsa Gottsche from collections made in the Azores and Madeira establishes a significant range extension for a taxon, known under several other names, which occurs in the southern Appalachian Mountains and in Costa Rica. Rycroft et al. (2001) described morphological and phytochemical characteristics of representative specimens of this liverwort. Phytochemically, P. retrorsa belongs to the 9,10-dihydrophenanthrene chemotype species (major stmctural type is that of compounds 449 and 450). 

Mastigophora diclados (Brid.) Nees, a liverwort that occurs in the mountains of tropical Asia, has been studied for its chemical constituents by Asakawa and his colleagues. Accessions from two disjunct sites in Malaysia were examined, one from Sabah State (1900-2500 m on Mt. Kinabalu) and one in West Malaysia from Pahang State (1500 m on Mt. Reskit). The East Malaysian material afforded compounds of the sort here exemplified by a-herbertenol [460] and mastifophorene-A [461]... 

The structure of a compound separated from the antifungal constituents of the Chinese liverwort Marchantia polymorpha L. (Marchantiaceae) was identified by H and 13C NMR spectroscopy and established to be 13,13 -0-isopropylidene-riccardin 17 <2006MI34>. The acetonide structure of 17 emerged from the 13C NMR spectra and HMBC correlations. For the structural elucidation of a new . 

The nor-ketone rudbeckianone (244) has been identified in Rudbeckia lacini-ata A very interesting new sesquiterpenoid ketone, (+)-bicyclohumulenone (245), has been isolated from the leafy liverwort Plagiochila acanthophylla subsp. japonica The structure and absolute stereochemistry of this compound were ascertained by X-ray crystallographic analysis of the mono-p-bromobenzoate of the derived triol (246). This ketone co-occurs with the two enantiomeric sesquiterpenoids (-)-maalioxide (247) and (+)-cyclocolerenone (248). 

A continuing investigation of the sesquiterpenoids from liverworts (Plagiochila species) has revealed the presence of more seco-aromadendrane compounds, namely plagiochilines A (652), B (653), C (654), D (655), E (656), and F (657). Plagiochilide (658) has been found in the Swiss species of P. asplenioides but not in the French version. The presumed precursor of these compounds, (-)-bicyclogermacrene (659), has also been identified in the extracts... 

In addition to the CD exciton chirality method, we have recently reported that the theoretical calculation of the CD spectra by the jt-electron SCF-CI-dipole velocity MO method8-l4 has become an important tool for determination of the absolute configuration of a variety of twisted and conjugated n-electron systems. In fact, we have recently determined the absolute stereochemistry of (8aS)-(+)-l,8a-dihydro-3,8-dimethylazulene 10, a labile biosynthetic intermediate for 1,4-dimethylazulene 11 isolated from a liverwort, by application of the MO method to the theoretical calculation of the CD spectra of the twisted tetraene system (8a/ )-12.15 In that case, we have also succeeded in the experimental verification of the absolute configuration theoretically determined, by comparison of the CD spectra of the natural product with those of synthetic chiral model compounds (8a5)-(+)-... 

Chemical investigation of the diethyl ether extract from the liverwort Corsinia coriandrina resulted in the isolation of a new 2-arylbenzofiiran compound called corsifuran C (87) whose structure has been confirmed by synthesis [56]. 

It is evident that the three new aromatics (208—210) isolated from the New Zealand liverwort Balantiopsis rosea stem from a bibenzyl. The structure of compound 209 was established by NMR and X-ray crystallographic analysis and the absolute configurations of these structures were determined by CD analysis [104]. 

Marchantins M-P (239-242) are the marchantin-type compounds discovered recently. Marchantins M-O (239-241) were isolated from the Taiwanese liverwort Reboulia hemisphaerica together with the previously known marchantinquinone and marchantin C (813) [129]. Marchantin N (240) is a marchantinquinone derivative. Marchantin P (242) together with riccardin G (243) was identified in Marchantia chenopoda cultivated in Venezuela [130]. 

New additions to the eudesmanolide family include (610)—(635).105 154 220 222-231,247,249,276-282 examination of liverwort species continues to reveal interesting new structures such as those of (+)-p-frullanolide (636) and (+)-brothenolide (637) from Frullania brotheri283 and (+)-crispatanolide (638) from Makinoa crispata.2Si The last compound is unique in the eudesmane field having a 8-lactone attached between C-7 and C-14. 

X-Ray crystallographic analysis has led to a revised cycloaromadendrane structure for (-)-myliol (619), a metabolite of the liverwort Mylia taylorii ° cf. Vol. 4, p. 135 Vol. 6, p. 90). More recent investigations have resulted in the isolation of an isomeric compound, (—)-dihydromylione A (620) from the same source. Independent studies have also revealed the widespread occurrence of a closely related hydrocarbon, anastreptene (177), in the essential oils of various liverworts Anastrepta oveadensis, Diplophyllum albicans, Barbilophozia species) cf. p. 

Bryophytes are divided into three classes, Musci, Hepaticae (liverwort) and Anthocerotae, which are known to include 14000,6000 and 300 species, respectively. Various kinds of biologically active compounds have been discovered from bryophytes. For instance there are compounds with hot or bitter taste, ichthyotoxicity, insect antifeedant, antiinflammatory, antimicrobial, antifungus and antitumor activities (1). In liverworts, there exist oil bodies, while in Musci, no oil bodies are present. This can help us to identify the liverworts. 

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