Chemical constituents of the genus Pithecellobium:a systematic review

Han Zhang, Zhiyang Yan, Xiaoxiao Huang＊

Department of Natural Products Chemistry, Shenyang Pharmaceutical University, Shenyang 110016, PR China

1 Introduction

Pithecellobium Mart, a perennial aiphyllium herb, is mainly distributed in tropical and subtropical regions, especially in tropical America.It was also found in Vietnam and India [1].There are four species distributed in China [2],including pithecellobium clypearia (Jack) Benth,Pithecellobium dulce (Roxb.) Benth, pithecellobium lucidum Benth, pithecellobium utile Chun & F. C.How. The leaves, stems, fruits and seeds of plants in Pithecellobium Mart have been used as Chinese folk medicine for the treatment of rheumatalgia, wounds,acute tonsillitis, acute gastroenteritis and bacterial dysentery [3].

Previous studies on the chemical components of the genus revealed the presence of flavonoids,triterpenoids, steroids, phenolic acids, lignans.Among the compounds, the presence of flavonoids may be the reason for its prominent biological activities especially antiviral potentials [4].Therefore, the further study on the chemical compositions of the genus will contribute to the development of new drugs and make full use of natural medicinal resources. This paper summarized the latest research progress of chemical compositions of this genus.

2 Research progress of chemical constituents

2.1 Flavonoids

As the typical constituents in Pithecellobium Mart, flavonoids are effective antioxidants and may protect against several chronic diseases [5], which are the most typical constituents in Pithecellobium Mart. Forty-one compounds have been isolated from the Pithecellobium Mart at present. Among them,most of the flavonoids are classified into six types on the basis of their chemical structural characteristics and skeletons. They are flavanols, flavanones,flavones, isoflavones, flavonols and anthocyanins.

2.1.1 Flavans

Twenty flavans have been isolated and identified from the Pithecellobium Mart at present,which mainly exist in the P. clypearia and P. dulce.They are (-)-epigallocatechin (1) [6], (-)-5,7,3',4',5'-pentahydroxyflavan (2) [6], (+)-catechin (3) [7,8],robinetinidol (4) [9], 3',4',7-trihydroxy-3,4-flavandiol (5) [9,10], 3',4',5',7-tetrahydroxyflavan-3-flavandiol (6) [9], (2R,3R)-7,8,3',4'-tetrahydroxydihydroflavonol (7) [11], (2R,3S)-5,7,3'-tri-omethyl-(-)-epicatechin (8) [11], (-)-epigallocatechin-7-gallate (9) [6], (-)-5,3',4',5'-tetrahydroxyflavan-7-gallate (10) [6-7, 12], (-)-(2R,3R)-epigallocatechin-3-O-gallate (11) [7], 7,3'-di-O-galloyltricetiflavan(12) [13,14], 7,4'-di-O-galloyltricetiflavan(13) [12-14], gallocatechin gallate (14) [8],epifisetinidol-4β-catechin (15), dimeric epicatechuns(16), bis-epifisetinidol-4β-catechin (17), fisetinidol-4β-catechin-epifisetinidol (18), trimeric epicatechuns(19), fisetinidol-4β-epicatechin-epifisetinidol(20) [15]. There are flavonoids with one or two galloyl groups in Pithecellobium Mart, such as compounds 9-14. In addition, several bisflavone were also found in this genus and mainly present in the methanol extract of P. dulce. Previous research showed that these bisflavones exhibited antibacterial activity [15]. Their structures are listed in Fig. 1.

Fig. 1 Flavans in Pithecellobium Mart

2.1.2 Flavones and flavonoid glycosides

It is reported that there are a number of flavones and flavonoid glycosides in Pithecellobium Mart,which mainly exist in P. clypearia and P. dulce.They are 5-hydroxy-3,7,3',4'-tetramethoxyflavone(21) [16], 5,4'-dihydroxy-3,7,3'-trimethoxyflavone(22) [16], luteolin (23) [11,16], kaempferol(24) [8,17], quercetin (25) [11], quercitin-3-O-α-L-rhamnpyranoside (26) [6,18], myricitin-3-O-α-L-rhamnpyranoside (27) [6,18], luteoloside (28) [18],kaempferol-3-Ο-α-L-rhamnosid (29) [19],3'-prenylapigenine-7-O-rutinoside (30) [20], homoflavoyadorinin-B (31), rhamnazin-4'-Ο-α-D-[apiosyl(1→2)glucoside] (32), flavoyadorinin B(33), rhamnazin-3,4'-di-O-glucoside (34) [21] (Fig.2).

Fig. 2 Flavones and flavonoid glycosides in Pithecellobium Mart

2.1.3 Chalcones, isoflavones and flavonoid derivatives

Two chalcones, two flavonoid derivatives and one isoflavone were isolated and identified from the Pithecellobium Mart, including clypesides A (35), clypesides B (36), genistein-4'-Ο-α-L-rhamnopyranoside (37) [21], pithecellobiumol A(38), pithecellobiumol B (39) [22] (Fig. 3).

Fig. 3 Chalcones, isoflavones and flavonoid derivatives in Pithecellobium Mart

2.2 Triterpenoids and steroids

Triterpenoids and steroids are another main chemical constituents of the genus. All triterpenoids in the genus are almost pentacyclic triterpenoid, with ursane and oleanane as the majority [2].

2.2.1 Pentacyclic triterpenoids

Eighteen oleananes and five ursanes were isolated and identified from the Pithecellobium Mart at present. They are listed in Table 1. The parent structure (I) and substituent groups of compounds are shown in Fig. 4. Chemical structures of ursanes are shown in Fig. 5.

Fig. 4 Parent structure (I) and substituent groups of triterpenoids from plants of Pithecellobium Mart

Table 1 Pentacyclic triterpenoids from the Pithecellobium Mart

Continued Table 1

Fig. 5 Chemical structures of compounds 58-61

2.2.2 Tetracyclic triterpenes

Seven tetracyclic triterpenes were isolated and identified from the P. clypearia, including â-Sitosterol (62), campesterol (63), stigmasterol(64) [16], á-spinasterol (65) [16,29], α-D-glucoside of α-spinasterol (66), 3-O-6'-O-palmitoyl-α-D-glucosyl-spinasta-7,22(23)-diene (67), 3-O-6'-O-stearoyl-α-D-glucosylspinasta-7,22(23)-diene(68) [30] (Fig. 6).

Fig. 6 Tetracyclic triterpenes in Pithecellobium Mart

2.3 Phenolic acids

Phenolic compounds are also important constituents. Polyphenolic compounds could affect on cells due to their antioxidant activities as well as their modulation of different pathways including signaling cascades, antiapoptotic processes and the formation of the amyloid β peptide [5].

Thirteen phenolic acids were isolated and identified from the Pithecellobium Mart, which mainly exist in the P. clypearia, including gallic acid(69) [6,11,18], ethyl gallate (70) [6,18,31], methyl gallate (71) [31], protocatechuic acid methy ester(72) [11], methyl 2-Ο-α-D-glucopyranosylbenzoate(73) [31], canthoside A (74) [31], clypearoside A(75) [32] (Fig. 7).

Fig. 7 Phenolic acids in Pithecellobium Mart

2.4 Lignans and phenylpropanoids

Lignans and phenylpropanoids have been found in this genus. They are divided into four different classes dependeding on different molecular structures. They are biphenyl derivatives, arylnaphthalenes, tetrahydrofurans,furofurans, which mainly exist in the P. clypearia.They are clypearianin A-G (76-82), (7'R,8'R)-7'-methoxyl strebluslignanol (83), magnolol(84), magnaldehyde (85), randaiol (86) [33],polystachyol (87), (+)-lyoniresinol-3-α-Ο-β-D-glucopyranoside (88), (-)-lyoniresinol-3-α-Ο-β-D-glucopyranoside (89), alangilignoside C (90),(+)-pinoresinol (91), lawsoniaside B (92), 3-(4β-D-glucopyranosyloxy-3-methoxy)-phenyl-2E-propenol(93), polygalatenoside E (94) [34], 3-(4-Hydroxy-3,5-dimethoxyphenyl)-1,2-propanediol(95),3-(4-Hydroxy-3-methoxyphenyl)-1,2-propanediol (96),4-Ο-β-D-glucopyranosyl-p-coumaric acid (97) [7],chlorogenic acid ethyl ester (98) [7], 4-Ο-α-D-glucopyranosyl-trans-p-coumaric acid (99) [7] (Fig.8).

Fig. 8 Lignans and phenylpropanoids in Pithecellobium Mart

3 Conclusion

Phytochemical researches demonstrated that the chemical compositions of Pithecellobium Mart included flavonoids, triterpenoids, steroids, phenolic acids, lignans and phenylpropanoids. The researchs showed that flavonoids, triterpenes and steroids were mainly chemical constituents of the genus and possessed potent biological activities, such as antiarrhythmic activiry, anti-oxidant, antibacterial,antiviral and so on. Therefore, further study of the chemical compositions and pharmacological activities of Pithecellobium Mart is of great significance. This paper provided crucial material for the further development and utilization of Pithecellobium Mart.

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China(81502954).

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