Professional Documents
Culture Documents
8 (2011)
REVIEW
Contents
1. Introduction
2. Chemical Constituents
2.1. Diterpenoids
2.1.1. Cassane Diterpenoids
2.1.2. Norcassane Diterpenoids
2.1.3. Rosane-Type Diterpenes
2.1.4. Other Diterpenes
2.2. Triterpenes
2.3. Flavonoids
2.3.1. Homoisoflavones
2.3.2. Chalcones
2.3.3. Flavonols
2.3.4. Flavanones
2.3.5. Isoflavanones
2.4. Aromatic Phenols
2.5. Organic Acids and Esters
2.6. Phenylpropanoids
2.7. Hydrocarbons and Alcohols
2.8. Glucosides
2.9. Peltogynoids
2.10. Anthraquinones
2.11. Alkaloids
2.12. Others
3. Biological Activities
3.1. Cytotoxic Activity
3.2. Antiproliferative Activity
3.3. Antimicrobial Activity
3.4. Antimalarial Activity
Table (cont.)
Table (cont.)
Table (cont.)
Table (cont.)
Table (cont.)
Table (cont.)
Table (cont.)
same source as the other norcassane-type diterpenes in 2006. Compound 142 has a 17-
norcassane skeleton with a unique C(1)¼O group and the relative configuration of 142
was determined by a difference NOE experiment [13]. Investigation of C. crista from
Myanmar resulted in the isolation of three new norcassane-type diterpenes, norcae-
salpinins MA – MC (143 – 145, resp.) in 2004 [21]. The sequence compound norcae-
salpinin MD (146) was reported in the following year with a similar skeleton as
norcaesalpinin F (142). Cheenpracha et al. reported two new norcassane diterpenes,
147 and 148, isolated from the stems and roots of C. crista, which differ from the
previously isolated diterpenes from the seed kernels [26].
2.1.3. Rosane-Type Diterpenoids. The sole rosane-type diterpene ent-11a-hydroxy-
rosa-5,15-diene (149) was isolated from the stems and roots of C. crista, and it exhibited
significant antimalaria activity with an ED50 value of 4.1 mg/ml [26].
2.1.4. Other Diterpenes. A new diterpene was isolated from the 95% EtOH extract
of the seeds of C. minax Hance. and was named minaxin B (150) [42]. It possesses a
unique structure that differs from all cassane diterpenes and norcassane diterpenes
mentioned above.
2.2. Triterpenes. From the CH2Cl2/MeOH 1 : 1 extracts of Argentinean legume C.
paraguariensis Burk. (Fabaceae), Woldemichael et al. isolated six triterpenes, 151 –
153, 156, and 157 [43]. A phytochemical study of the stem of the C. minax and a
subsequent reduction afforded two friedelane triterpenoids, 154 and 155, whose
structures were elucidated by spectroscopic methods [23]. Stigmasterol (158) was
isolated together with other five cassane furanoditerpenes from the seeds of C. minax.
Its structure was verified by X-ray analysis for the first time [22]. From the light
petroleum ether extract of C. benthamiana, Dickson et al. isolated two triterpenes, 159
1390 CHEMISTRY & BIODIVERSITY – Vol. 8 (2011)
and 160, as well as stigmastenone and b-sitosterol [27]. Udenigwe et al. isolated a new
sterol, 17-hydroxycampesta-4,6-dien-3-one (161), with other two known sterols 13,14-
secostigmasta-5,14-dien-3a-ol (162) and 13,14-secostigmasta-9(11),14-dien-3a-ol (163)
[19]. Compounds 162 and 163 have combined C/D rings differing from those of the
compound 161. The hypothetic biogenetic pathway was proposed as depicted in
Scheme 1: stigmast-5-en-3a-ol is oxidized at C(14) and forms a new OH group which
leads to an intermediate carbonyl.
Scheme 1. Proposed Biogenetic Scheme for the Formation of the C/D seco Ring of 162, Starting from
Stigmast-5-en-3a-ol
Sappan Lignum, and separated them as isomeric hexamethyl ethers [65]. Chemical and
spectral data of the hexamethyl ethers indicated that 216/217 might be transformed to
brazilin (203) and protosappanin B (214), on treatment with NaBH4 in alkali solution
via brazilein (206) and protosappanin C (221) (Scheme 2) [65]. In 2005, protosappanin
E-2 (217) was isolated as single component from this plant family and was identified for
the first time. Compound 217 can be formally split into two distinct groups based on
analysis of its spectroscopic data, namely into protosappanin B (214) and brazilin (203)
[52]. The same analytic method was used for the identification of neoprotosappanin
(218) and neosappanone A (219). Compound 218 contains two brazilin monomer units,
linked to each other through a new bond from C(7) of one unit to C(2) in the other,
while 219 was derived from caesalpin J (208). A possible biogenetic path is proposed in
Scheme 3 [66].
Washiyama et al. isolated protosappanin D (222) from the Sappan Lignum with
compounds 212, 214, 217, and 221 [56]. Shu isolated two new dimers, 223 and 224, from
C. sappan, together with a stilbene, 225, and many compounds which were previously
mentioned [18]. (þ)-(8S,8’S)-Bisdihydrosiringenin (226) was isolated, together with
the new 3-benzylchroman 182 [55]. Bioassay-guided fractionation of a MeOH extract
of Sappan Lignum provided the novel aromatic compound caesalpine J (227), which
was shown to be inactive against glutamate-induced cytotoxicity in HT22 cells [54].
Compounds 228 and 229 were isolated from the C. millettii in 2007 [45].
Fractionation of C. paraguariensis afforded the novel benzoxecin derivatives 230 and
231, but they did not show any biological activity [43]. Nozaki et al. isolated the unique
chalcone derivative 232 from the stems of C. ferrea Mart. The structure was
determined on the basis of 2D-NMR spectroscopy to be a chalcone trimer, linked by a
cyclobutane ring [68]. The new compound 233 was isolated from the C. decapetala for
the first time [69], and compound 234 was obtained from of the stem of C. pulcherrima
[2].
2.5. Organic Acids and Esters. Benzyl 2,6-dimethoxybenzoate (235) was isolated
from the air-dried leaves of C. pulcherrima and shown to be active against several
bacteria and fungi [24]. Compounds 236 – 239 were obtained from the dried pods of C.
spinosa by Kondo et al. in 2006, and 236 and 237 were new compounds from the genus
[70]. Shu isolated dimethyl adipate (240) from C. sappan [18]. Studies on the chemical
constituents of C. millettii afforded compounds 241 – 246, and compounds 242 and 243
were also isolated from C. ferrea in 2002 [45] [71]. Yuan et al. obtained ethyl 2,5-
dihydroxybenzoate (247) from the seeds of C. minax [40]. Zhang et al. isolated the
long-chain compound 248 from the stem of C. decapetala [69]. Compounds 249 and 250
were isolated from C. sappan in 2008 and 2009, respectively [54] [55].
1394 CHEMISTRY & BIODIVERSITY – Vol. 8 (2011)
Scheme 4. Hypothetical Biosynthetic Relationship between Sappanchalcone 178 and 203, and the Related
Compounds
2.6. Phenylpropanoids. Two coumarins, 251 and 252, and two lignanoids, 253 and
254, were isolated from C. ferrea and C. sappan [18] [72].
2.7. Hydrocarbons and Alcohols. The only alkene, 255, was isolated from C.
decapetala in 2005 [36]. Studies on the chemical constituents of C. millettii afforded the
two long-chain alkanes, 256 and 257, as well as a fatty alcohol 258 [45].
2.8. Glucosides. Studies on the chemical constituents of C. millettii Hook yielded a
triterpene named daucosterol (259) [45]. Woldemichael isolated three glucopyrano-
sides, 260 – 262, from the CH2Cl2/MeOH extract of C. paraguariensis [43].
Astragalin (263) was isolated from the leaves of C. decapetala [36]. Chen isolated
hyperoside (264) and tamarixetin 3-O-{6’’-O-[(E)-caffeoyl]}-b-d-galactopyranoside
(265) from the aerial part of C. millettii [45]. Two new glycosyl phenylpropenoid acids,
(Z)-4-(b-glucopyranosyloxy)-7-hydroxycinnamic acid (266) and (Z)-4-(b-glucopyra-
nosyloxy)-8-hydroxycinnamic acid (267) were isolated from the leaves of C. pyrami-
CHEMISTRY & BIODIVERSITY – Vol. 8 (2011) 1395
dalis in 2000, with the same styrene skeleton but differing in the location of the OH
group [73].
2.9. Peltogynoids. Only two peltogynoids, 268 and 269, were isolated from the stem
part of C. pulcherrima, and their structures were deduced by their spectral data [46].
2.10. Anthraquinones. A benzoquinone, 270, and a naphthoquinone, 271, were
isolated from C. pulcherrima and C. sappan, respectively [46] [74].
2.11. Alkaloids. Only one alkaloid, caffeine (272), was isolated from the fruit of C.
minax for the first time [64].
2.12. Others. Caryophyllene oxide (273) and spathulenol (274) were obtained from
the leaves of C. pulcherrima, and the latter was also found in the leaves of C. decapetala
together with the 4,5-epoxycaryophyll-8(14)-ene (275) [16] [36]. In addition, teucladiol
(279) and a-cadinol (280) were isolated from the stem of C. pulcherrima [2]. Udenigwe
et al. isolated pipataline (276) from the EtOH extract of the bark of C. bonduc [19].
From Sappam Lignum, Shu isolated 3,7-dihydroxychroman-4-one (277) [18]. Resver-
atrol (278) was isolated from the aerial part of C. millettii [45].
4. Conclusions. – Plants of the genus Caesalpinia are widely distributed all over the
world, and many species of this genus have been used as traditional herbal medicines.
Compounds isolated from the genus display powerful biological activities and have
potency to be new defensive agents against several kinds of diseases. However,
questions arose concerning the structureactivity relationships and elucidation of the
action mechanism, since compounds belonging to the same skeleton type displayed
different levels of activity against the same antigen. Further studies to explore the
mechanism at the molecular level and to exploit other types of constituents are
necessary.
We are grateful for the financially supports from the Scientific Research Foundation for the Returned
Overseas Chinese Scholars of Hebei Province (2006-02) and the Scientific Research Foundation of Hebei
Province (08B032 and C2010000489). We also wish to extend our sincere thanks to Syngenta Ltd. (2008-
Hebei Medical University-Syngenta-02), National Natural Science Foundation of China (81072551), and
grant-in-aid from the Japan Society for the Promotion of Science (No. 22580112) for the financial support.
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