Chemical Constituents of Plants from the Genus Caesalpinia

REVIEW

Chemical Constituents of Plants from the Genus Caesalpinia

by Ming Wua), Yu-Fang Wanga), Man-Li Zhanga), Chang-Hong Huoa), Mei Dongb), Qing-Wen Shi*a),and Hiromasa Kiyota*c)

a) School of Pharmaceutical Sciences, Hebei Medical University, 361 Zhongshan East Road,Shijiazhuang 050017, P. R. China (phone: þ86-311-6265634; e-mail: [email protected])b) Department of Forensic Medicine, Hebei Medical University, Shijiazhuang 050017, P. R. China

c) Laboratory of Applied Bioorganic Chemistry, Graduate School of Agricultural Sciences, TohokuUniversity, 1-1 Tsutsumidori-Amamiya, Aoba-ku, Sendai, 981-8555, Japan

(phone/fax: þ81-22-717-8785; e-mail: [email protected])

Contents

1. Introduction2. Chemical Constituents

2.1. Diterpenoids2.1.1. Cassane Diterpenoids2.1.2. Norcassane Diterpenoids2.1.3. Rosane-Type Diterpenes2.1.4. Other Diterpenes

2.2. Triterpenes2.3. Flavonoids

2.3.1. Homoisoflavones2.3.2. Chalcones2.3.3. Flavonols2.3.4. Flavanones2.3.5. Isoflavanones

2.4. Aromatic Phenols2.5. Organic Acids and Esters2.6. Phenylpropanoids2.7. Hydrocarbons and Alcohols2.8. Glucosides2.9. Peltogynoids2.10. Anthraquinones2.11. Alkaloids2.12. Others

3. Biological Activities3.1. Cytotoxic Activity3.2. Antiproliferative Activity3.3. Antimicrobial Activity3.4. Antimalarial Activity

CHEMISTRY & BIODIVERSITY – Vol. 8 (2011)1370

� 2011 Verlag Helvetica Chimica Acta AG, Z�rich

3.5. Immunosuppressive and Anti-Inflammatory Activity3.6. Antiviral Activity

4. Conclusions

1. Introduction. – The genus Caesalpinia (Leguminosae) comprises ca. 100 species,distributed widely in tropical and subtropical regions, and ca. 17 species of the genus arewidespread in China, and 14 species of the genus, for instance, C. decapetala and C.sappan L. [1] have long been used in Chinese traditional medicine for the treatment ofrheumatism and inflammatory diseases. Leaves, barks, and roots of C. pulcherrimaSwartz is used to alleviate fungal infection and to reduce fever [2]. Plants of the genusCaesalpinia have proven to be a rich source of cassane furanoditerpenes and othercompounds such as norcassane diterpenoids, triterpenes, flavonoids, etc.

In this review, we compile the phytochemical progress and list all the compoundsisolated from the genus Caesalpinia over the past few decades. Some biologicalactivities of compounds isolated from this genus in recent years are also included.

2. Chemical Constituents. – The reported chemical constituents from the genusCaesalpinia so far are in total 280 compounds, including diterpenes, triterpenes,flavonoids, aromatic phenols, phenylpropanoids, and some others. Their structures areshown below, and their names and the corresponding plant sources are collected in theTable. Diterpenoids are the predominant constituents within the genus of Caesalpinia.

2.1. Diterpenoids. 2.1.1. Cassane Diterpenoids. Cassane diterpenoids isolated fromthe genus Caesalpinia can be classified into five basic skeleton types [75]: i)tricarbocyclic derivatives fused with a furan ring, 1– 86 [2] [3– 28]; ii) tricarbocyclicderivatives fused with an a,b-butenolide, 87– 107 [2] [4] [25] [29 – 35]; iii) tricarbocyclicderivatives with cleavage of the furan ring, 108– 113 [15] [17] [21] [26] [36]; iv)rearranged furanoditerpenoids with migration of the Me group at C(4) to C(3),114– 116 [11] [37]; and v) furanoditerpenoid lactones constructed from ring closureinvolving the O-atoms bridged to C(7) and C(17), 117– 127 [6] [12] [13] [22] [23] [38][39] [75]. In 2004, Kalauni et al. reported five new cassane diterpenes, 38 –41 and 110,compound 110 having a cleaved furan ring and with a bridge from C(7) to C(17) [21]. Inaddition, in 2008, eleven cassane diterpenes were isolated from the seeds of C. sappanL. for the first time from a natural source, revealing another kind of unusual skeleton.Compounds 128– 133 with an additional oxa bridge between C(19) and C(20),while compounds 134– 135 are endowed with an oxa bridge between C(11) and C(20)[28].

2.1.2. Norcassane Diterpenoids. Investigation of the constituents from seeds of C.minax, a new norcassane diterpene, named norcaesalnin E (136), was isolated for thefirst time from this plant [40]. In 2003, three novel norcassane-type diterpenes wereobtained from the seed kernels of C. crista with an unprecedented C-skeleton.Norcaesalpinins A and B (137 and 138, resp.) have a 17-norcassane skeleton, whilenorcaesalpinin C (141) possesses a 16-norcassane skeleton [41]. Two years later, Linnet al. isolated two new norcassane-type diterpenes, 139 and 140, named norcaesalpininsD and E, respectively, with the 17-norcassane skeleton, from the same plant [6].Norcaesalpinin F (142), another new norcassane-type diterpene, was isolated from the

CHEMISTRY & BIODIVERSITY – Vol. 8 (2011) 1371


Table. Chemical Constituents of Plants from the Genus Caesalpinia

No. Name Plant Part Ref.

DiterpenoidsCassane Diterpenoids

1 6b-Cinnamoyl-7b-hydroxyvouacapen-5a-ol

C. pulcherrima root [3] [4]

stem [2]2 Vouacapen-5a-ol C. pulcherrima root [3]3 8,9,11,14-Didehydrovouacapen-5a-ol C. pulcherrima root [3]4 Caesalpin F C. bonducella seed [5]

C. crista seed kernel [6]5 e-Caesalpin C. minax seed [7]

C. bonducella [5]6 Caesaljapin C. decapetala root [8]7 Caesaldekarin B C. major root [9]8 Caesaldekarin D C. major root [9]9 Caesaldekarin E C. major root [9]

C. crista seed kernel [10]C. crista seed kernel [11]

10 Bonducellpin A C. bonduc root [12]11 Bonducellpin B C. bonduc root [12]12 Bonducellpin C C. bonduc root [12]


13 Pulcherrimin C C. pulcherrima root [14]C. pulcherrima stem [2]

14 Pulcherrimin D C. pulcherrima root [14]15 Pulcherrimin B C. pulcherrima root [14]16 Caesaldekarin A C. bonduc root [15]

C. pulcherrima leaves [16]17 Caesaldekarin H C. bonduc root [15]18 Demethylcaesaldekarin C C. bonduc root [15]19 Caesaldekarin I C. bonduc root [15]20 Caesaldekarin C C. boducella root [17]21 Caesaldekarin F C. boducella root [17]

C. sappan heartwood [18]22 Caesaldekarin J C. bonduc root [15]

C. bonduc bark [19]23 Caesaldekarin K C. bonduc root [15]24 14-Deoxy-e-caesalpin C. major seed kernel [20]25 Caesalmin C C. minax seed [21]

C. crista seed kernel [10] [11] [22]26 Caesalmin D C. minax seed [22] [23]27 Caesalmin E C. minax seed [22] [23]

C. crista seed kernel [21]28 Caesalmin F C. minax seed [22] [23]29 Caesalmin H C. minax seed [23]30 Isovouacapenol A C. pulcherrima leaves [16] [24]31 Isovouacapenol B C. pulcherrima leaves [24]32 Isovouacapenol C C. pulcherrima leaves [24]

root [4]stem [2]


Table (cont.)


33 Isovouacapenol D C. pulcherrima leaves [24]34 Isovouacapenol E C. pulcherrima leaves [16]35 Pulcherrimin A C. pulcherrima root [4]36 Pulcherrimin E C. pulcherrima root [4]

stem [2]37 Pulcherrimin F C. pulcherrima root [4]38 Caesalpinin MA C. crista seed kernel [21]39 Caesalpinin MB C. crista seed kernel [21]40 Caesalpinin MC C. crista seed kernel [21]41 Caesalpinin MD C. crista seed kernel [21]42 2-Acetoxycaesaldekarin E C. crista seed kernel [10] [11] [21]43 Caesalpinin C C. crista seed kernel [6] [13] [21]44 14(17)-Dehydrocaesallpin F C. crista seed kernel [6] [21]45 Caesalpinin E C. crista seed kernel [21] [25]46 7-Acetoxybonducellpin C C. crista seed kernel [6] [10]

[13] [21]47 2-Acetoxy-3-deacetoxycaesaldekarin E C. crista seed kernel [11]48 1-Deacetylcaesalmin C C. crista seed kernel [11]49 1-Deacetoxy-1-oxocaesalmin C C. crista seed kernel [11]50 Caesalpinin MF C. crista seed kernel [10]51 Caesalpinin MG C. crista seed kernel [10]52 Caesalpinin MH C. crista seed kernel [10]53 Caesalpinin MI C. crista seed kernel [10]54 Caesalpinin MJ C. crista seed kernel [1055 Caesalpinin MK C. crista seed kernel [10]56 Caesalpinin MO C. crista seed kernel [11]57 Caesalpinin MP C. crista seed kernel [11]58 Caesalpinin F C. crista seed kernel [6]59 Nontaepeenin A C. crista stem root [26]60 Nontaepeenin B C. crista stem root [26]61 Taepeenin A C. crista stem root [26]62 Taepeenin B C. crista stem root [26]63 Taepeenin C C. crista stem root [26]64 Taepeenin D C. crista stem root [26]65 Taepeenin E C. crista stem root [26]66 Taepeenin H C. crista stem root [26]67 Taepeenin I C. crista stem root [26]68 Vinhaticoic acid C. crista stem root [26]69 Methyl vinhaticoate C. crista stem root [26]70 Caesalpinin J C. crista seed kernel [13]71 Caesalpinin K C. crista seed kernel [13]72 Caesalpinin L C. crista seed kernel [13]73 Caesalpinin N C. crista seed kernel [13]74 Caesalpinin M C. crista seed kernel [13]75 Caesalpinin P C. crista seed kernel [13]76 Benthaminin 1 C. benthamiana root bark [27]77 Benthaminin 2 C. benthamiana root bark [27]78 Deoxycaesaldekarin C C. benthamiana root bark [27]79 z-Caesalpin C. sappan heartwood [18]80 Phanginin I C. sappan seed [28]


Table (cont.)


81 Phanginin J C. sappan seed [28]82 Phanginin K C. sappan seed [28]83 6b-Acetoxy-17-methylvoucapa-8(14),9(11)-diene C. bonduc whole plant [25]84 Pulcherrin A C. pulcherrima stem [2]85 Pulcherrin B C. pulcherrima stem [2]86 Pulcherrin C C. pulcherrima stem [2]87 Neocaesalpin B C. bonduc seed [29]88 Neocaesalpin C C. bonduc seed [29]89 Neocaesalpin D C. bonduc seed [29]90 Spirocaesalmin C. minax seed [30]91 Neocaesalpin E C. pulcherrima root [4]92 Neocaesalpin F C. pulcherrima root [4]93 Neocaesalpin G C. pulcherrima root [4]94 Neocaesalpin H C. crista leaves [31]95 Neocaesalpin I C. crista leaves [31]96 Taepeenin F C. crista stem root [26]97 Caesalpinolide A C. bonduc marine creeper [32]98 Caesalpinolide B C. bonduc marine creeper [32]99 Neocaesalpin W C. bonduc seed [33]100 Neocaesalpin L1 C. minax fruit [34]101 Caesalpinolide C C. bonduc whole plant [25]102 Caesalpinolide E C. bonduc whole plant [25]103 Caesalpinolide D C. bonduc whole plant [25]104 1a,6a,7b-Triacetoxy-14b-hydroxy-12a-

methoxycass-13(15)-en-16,12-olideC. minax seed [35]

105 Neocaesalpin P C. pulcherrima stem [2]106 Neocaesalpin Q C. pulcherrima stem [2]107 Neocaesalpin R C. pulcherrima stem [2]108 Caesaldekarin G C. bonducella root [17]109 Caesaldekarin L C. bonduc root [15]110 Caesalpinin ME C. crista seed kernel [21]111 Caesalpinin ML C. crista seed kernel [17]112 Caesaldecan C. decapetala leaves [36]113 Taepeenin G C. crista stem root [26]114 Caesalpinin C. bonducella root [37]115 Caesalpinin MM C. crista seed kernel [11]116 Caesalpinin MN C. crista seed kernel [11]117 Bonducellpin D C. minax seed [23]

C. bonduc root [12]118 Caesalmin A C. minax seed [22]119 Caesalmin B C. minax seed [22] [23]


120 Caesalmin G C. minax seed [22]121 Macrocaesalmin C. minax seed [3]122 Caesalpinin D C. crista seed kernel [6] [13]123 Caesalpinin G C. crista seed kernel [6]124 Caesalpinin H C. crista seed kernel [13]125 Caesalpinin O C. crista seed kernel [13]126 Caesalpinin I C. crista seed kernel [13]


Table (cont.)


127 Minaxin A C. minax fruit [38] [39]128 Phanginin A C. sappan seed [28]129 Phanginin B C. sappan seed [28]130 Phanginin C C. sappan seed [28]131 Phanginin D C. sappan seed [28]132 Phanginin E C. sappan seed [28]133 Phanginin F C. sappan seed [28]134 Phanginin G C. sappan seed [28]135 Phanginin H C. sappan seed [28]

Norcassane Diterpenoids136 Norcaesalnin E C. minax seed [40]137 Norcaesalpinin A C. crista seed kernel [6] [41]138 Norcaesalpinin B C. crista seed kernel [6] [41]139 Norcaesalpinin D C. crista seed kernel [6]140 Norcaesalpinin E C. crista seed kernel [6] [11]141 Norcaesalpinin C C. crista seed kernel [6] [41]142 Norcaesalpinin F C. crista seed kernel [13]143 Norcaesalpinin MA C. crista seed kernel [21]144 Norcaesalpinin MB C. crista seed kernel [21]145 Norcaesalpinin MC C. crista seed kernel [21]146 Norcaesalpinin MD C. crista seed kernel [10]147 Nortaepeenin A C. crista stem root [26]148 Nortaepeenin B C. crista stem root [26]

Rosane-Type Diterpenes149 ent-11b-Hydroxyrosa-5,15-diene C. crista stem root [26]

Other Diterpenoid150 Minaxin B C. minax fruit [42]

seed [38]

Triterpenes151 Betulinic acid C. paraguariensis aerial part [43]]152 3-O-[(E)-4-Hydroxycinnamoyl]-

betulinic acidC. paraguariensis aerial part [43]

153 Lupeol C. decapetala leaves [36]C. paraguariensis aerial part [43]C. ferruginea stem bark [44]

154 Epifriedelinol C. minax seed [23]155 Friedelin C. minax seed [23]156 Oleanolic Acid C. paraguariensis aerial part [43]157 3-O-[(E)-4-Hydroxycinnamoyl]-

oleanolic acidC. paraguariensis aerial part [43]

158 Stigmasterol C. minax seed [22]C. decapetala leaves [36]

159 Stigmastenone C. benthamiana root bark [27]160 b-Sitosterol C. millettii aerial part [45]

C. benthamiana root bark [27]161 17-Hydroxycampesta-4,6-dien-3-one C. bonduc bark [19]162 13,14-Secostigmasta-5,14-dien-3a-ol C. bonduc bark [19]163 13,14-Secostigmasta-9(11),14-dien-3a-ol C. bonduc bark [19]


Table (cont.)


FlavonoidsHomoisoflavones

164 Bonducellin C. pulcherrima stem [2] [46–48]aerial part [45] [49]

165 Isobonducellin C. pulcherrima aerial part [47]cultured cells [48] [49]

166 2’-Methoxybonducellin C. pulcherrima cultured cells [49]167 8-Methoxybonducellin C. pulcherrima stem [46]

C. sappan heartwood [50]C. millettii aerial part [45]

168 8-Methoxyisobonducellin C. millettii aerial part [45]169 7-Hydroxy-3-(4-hydroxybenzylidene)-

chroman-4-oneC. sappan heartwood [50]

170 3,7-Dihydroxy-3-(4-hydroxybenzyl)-chroman-4-one

C. sappan heartwood [50]

171 3,4,7-Trihydroxy-3-(4-hydroxybenzyl)-chroman

C. sappan heartwood [50]

172 3’-Deoxysappanol C. sappan heartwood [50–52]173 3’-Deoxy-4-O-methylsappanol C. sappan heartwood [52]174 4-O-Methylsappanol C. sappan heartwood [52–54]175 4-O-Methylepisappanol C. sappan heartwood [52–54]176 Sappanone B C. sappan heartwood [52] [53] [55]177 3-Deoxysappanone B C. sappan heartwood [18] [52]

[53] [55]178 Sappanchalcone C. sappan heartwood [18] [52]

[55] [56]179 Sappanol C. sappan heartwood [52]180 3’-Deoxy-4-O-methylepisappanol C. sappan heartwood [55]181 3’-O-Methylsappanol C. sappan heartwood [51] [53]182 Episappanol C. sappan heartwood [51] [53]183 3’-O-Methylepisappanol C. sappan heartwood [51] [53]184 3’-Deoxysappanone B C. sappan heartwood [51]185 Eucomin C. millettii aerial part [45]186 Intricatinol C. millettii aerial part [45]187 Caesalpinianone C. bonduc bark [57]188 6-O-Methylcaesalpinianone C. bonduc bark [57]

Chalcones189 4’-Methylisoliquiritigenin C. pulcherrima stem [46]190 4,4’-Dihydroxy-2’-methoxychalcone C. sappan heartwood [50]191 2’-Hydroxy-2,3,4’,6’-

tetramethoxychalconeC. pulcherrima aerial part [47] [48]

192 Isoliquiritigenin C. millettii aerial part [45]193 3-Deoxysappanchalcone C. sappan heartwood [55]

Flavonols194 Quercetin C. sappan heartwood [50]

C. decapetala leaves [36]195 Ombuin C. sappan heartwood [50]196 Rhamnetin C. sappan heartwood [18] [50]197 C. sappan heartwood [18]


Table (cont.)


3,8-Dihydroxy-4,10-dimethoxy-7-oxo[2]benzopyrano[4,3-b]benzopyranFlavanones

198 5,7-Dimethoxyflavanone C. pulcherrima aerial part [47] [48]199 5,7-Dimethoxy-3’,4’-(methylenedioxy)-

flavanoneC. pulcherrima aerial part [47] [48]

200 Liquiritigenin C. millettii aerial part [45]

Isoflavanones201 Dihydrobonducellin C. pulcherrima cultured cell [49]202 2’-Methoxydihydrobonducellin C. pulcherrima cultured cell [49]

Aromatic Phenols203 Brazilin C. sappan heartwood [18] [51–53]

[55] [56]204 3’-O-Methylbrazilin C. sappan heartwood [51–53] [55]205 Hematoxylin C. sappan heartwood [58]206 Brazilein C. sappan heartwood [18] [55]

[59] [60]207 Brazilide A C. sappan heartwood [18] [61]208 Caesalpin J C. sappan heartwood [62]209 Caesalpin P C. sappan heartwood [63]210 3-{[4,5-Dihydroxy-2-(hydroxymethyl)phenyl]-

2,3-dihydrobenzofuran-3,6-diolC. sappan bark [64]

211 1’,4’-Dihydrospiro{benzofuran-3(2H),3’-[3H] [2]benzopyran}-1’,6’,6’,7’-tetraol

C. sappan bark [64]

212 Protosappanin A C. sappan heartwood [18] [52] [55][56] [60] [62]

213 Protosappanin A dimethyl acetal C. sappan heartwood [52]214 Protosappanin B C. sappan heartwood [52]215 Protosappanin C dimethyl acetal C. sappan heartwood [52]216 Protosappanin E-1 C. sappan heartwood [65] [56]217 Protosappanin E-2 C. sappan heartwood [52]218 Neoprotosappanin C. sappan heartwood [52]219 Neosappanone A C. sappan heartwood [66] [52]220 Isoprotosappanin B C. sappan heartwood [55]221 Protosappanin C C. sappan heartwood [18] [56]222 Protosappanin D C. sappan heartwood [56]223 Neocaesalpin A C. sappan heartwood [18]224 Neocaesalpin B C. sappan heartwood [18]225 (E)-4,4’-Dihydroxy-3,3’-dimethoxystilbene C. sappan heartwood [18]226 (þ)-(8S,8’S)-Bisdihydrosiringenin C. sappan heartwood [55]227 Caesalpine J C. sappan heartwood [54]228 Bergenin C. millettii aerial part [45]

C. digyna root [67]229 11-O-Galloylbergenin C. millettii aerial part [45]230 Bilobetin C. paraguariensis aerial part [43]231 Caesalpinol C. paraguariensis aerial part [43]232 Pauferrol A C. ferrea stem [68]233 C. decapetala stem [69]


Table (cont.)


6’-Hydroxy-3,4-(1’’-hydroxyepoxy-propane)-2’,3’(1’’’b-hydroxy-2’’’-carbonyl-cyclobutane)-1,1’-biphenyl

234 7-Hydroxycadalene C. pulcherrima stem [2]

Organic Acids and Esters235 Benzyl 2,6-dimethoxybenzoate C. pulcherrima leaves [24]236 4,5-Di-O-galloylquinic acid methyl ester C. spinosa pod [70]237 3,4,5-Tri-O-galloylquinic acid methyl ester C. spinosa pod [70]238 3,4-Di-O-galloylquinic acid C. spinosa pod [70]239 3,4,5-Tri-O-galloylquinic acid C. spinosa pod [70]240 Dimethyl adipate C. sappan heartwood [18]241 Docosyl caffeate C. minax seed [45]242 Gallic acid C. ferrea fruit [71]

C. millettii aerial part [45]243 Methyl gallate C. ferrea fruit [71]

C. millettii aerial part [45]244 Digallic acid C. millettii aerial part [45]245 Tetragallic acid C. millettii aerial part [45]246 Tetragallicin C. millettii aerial part [45]247 Ethyl 2,5-dihydroxybenzoate C. minax reed [40]248 Octacosyl 3,5-dihydroxycinnamate C. decapetala stem [69]249 Palmitic acid C. sappan heartwood [55]250 Pluchoic acid C. sappan heartwood [54]251 Ellagic acid C. ferrea seed [72]

C. millettii aerial part [45]252 2-(2,3,6-Trihydroxy-4-carboxyphenyl)-

ellagic acidC. ferrea fruit [72]

253 (�)-Syringaresinol C. sappan heartwood [18]254 (� )-Lyoniresinol C. sappan heartwood [18] [55]255 Squalene C. decapetala leaves [36]256 Hentriacontane C. millettii aerial part [45]257 Nonacosyl alcohol C. millettii aerial part [45]258 Tritriacontane C. millettii aerial part [45]

Glucosides259 Daucosterol C. millettii aerial part [45]260 Stigmast-5-ene-3b-glucopyranoside C. paraguariensis aerial part [43]261 Stigmast-5-ene 3b-6’-palmitoylgluco-

pyranosideC. paraguariensis aerial part [43]

262 Stigmast-5-ene 3b-6’-stearoylgluco-pyranoside

C. paraguariensis aerial part [43]

263 Astragalin C. decapetala leaves [36]264 Hyperoside C. millettii aerial part [45]265 Tamarixetin 3-O-[6’’-O-(E)-caffeoyl]-

b-d-galactopyranosideC. millettii aerial part [45]

266 (Z)-4-(b-Glucopyranosyloxy)-b-hydroxycinnamic acid

C. pyramidalis leaves [73]

267 (Z)-4-(b-Glucopyranosyloxy)-a-hydroxycinnamic acid

C. pyramidalis leaves [73]

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 142was determined by a difference NOE experiment [13]. Investigation of C. crista fromMyanmar 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 asnorcaesalpinin 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 thepreviously 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 exhibitedsignificant 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 extractof the seeds of C. minax Hance. and was named minaxin B (150) [42]. It possesses aunique structure that differs from all cassane diterpenes and norcassane diterpenesmentioned 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 asubsequent reduction afforded two friedelane triterpenoids, 154 and 155, whosestructures were elucidated by spectroscopic methods [23]. Stigmasterol (158) wasisolated 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 lightpetroleum ether extract of C. benthamiana, Dickson et al. isolated two triterpenes, 159


Table (cont.)


Peltogynoids268 Pulcherrimin C. pulcherrima stem [46]269 6-Methoxypulcherrimin C. pulcherrima stem [46]

Anthraquinones270 2,6-Dimethoxybenzoquinone C. pulcherrima stem [46]271 5-Hydroxy-1,4-naphthoquinone C. sappan heartwood [74]

Alkaloid272 Caffeine C. minax fruit [38]

Others273 Caryophyllene oxide C. pulcherrima leaves [16]274 Spathulenol C. pulcherrima leaves [16]

C. decapetala leaves [36]275 4,5-Epoxycaryophyll-8(14)-ene C. decapetala leaves [36]276 Pipataline C. bonduc bark [19]277 3,7-Dihydroxychroman-4-one C. sappan heartwood [18]278 Resveratrol C. millettii aerial part [45]279 Teucladiol C. pulcherrima stem [2]280 a-Cadinol C. pulcherrima stem [2]

and 160, as well as stigmastenone and b-sitosterol [27]. Udenigwe et al. isolated a newsterol, 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 thecompound 161. The hypothetic biogenetic pathway was proposed as depicted inScheme 1: stigmast-5-en-3a-ol is oxidized at C(14) and forms a new OH group whichleads to an intermediate carbonyl.

2.3. Flavonoids. 2.3.1. Homoisoflavones. Several homoisoflavones have beenisolated from the genus Caesalpinia. From the stem of C. pulcherrima Swartz,McPherson et al. isolated a homoisoflavone, bonducellin (164), and a new derivative, 8-methoxybonducellin (167), in 1983 [46]. Then, many derivatives of bonducellin wereisolated from the genus. In 2003, investigation of the aerial parts of the same plantafforded 164 and another derivative, isobonducellin (165). Compound 165 was found tohave a (Z)-C(3)¼C(9) bond differing from bonducellin [47]. 2’-Methoxybonducellin(166) was isolated from C. pulcherrima cultured cells co-incubated with cork tissue[49]. Chen isolated another derivative of bonducellin from C. millettii, compound 168,with a skeleton similar to that of isobonducellin (165), and compounds 185 and 186were isolated at the same time [45]. Three new homoisoflavonoids, 169– 171, wereisolated from the heartwood of C. sappan [17]. Investigation of the MeOH extract ofVietnamese C. sappan afforded a series of homoisoflavonoids, including 172–179 [50–55]. In 2008, Fu et al. isolated the new 3-benzylchroman derivative 180 from C. sappan[55]. Namikoshi et al. isolated compounds 181– 184 from the dried heartwood of C.sappan [51] [53]. Phytochemical studies on the EtOH extracts of C. bonduc (Fabaceae)


Scheme 1. Proposed Biogenetic Scheme for the Formation of the C/D seco Ring of 162, Starting fromStigmast-5-en-3a-ol

yielded two new flavonoids, caesalpinianone (187), and 6-O-methylcaesalpinianone(188). Their skeletons were demonstrated to be homoisoflavonoids [57].

2.3.2. Chalcones. Five chalcones were isolated from the genus Caesalpinia, and theirstructures were established as 189– 193 [45 – 47] [50] [55].

2.3.3. Flavonols. From the dried heartwood of C. sappan, Namikoshi et al. obtainedthree flavonols, quercetin (194), ombuin (195), and rhamnetin (196) [50]. Studies onthe chemical constituents of C. sappan also afforded a new flavonol, 197, with a new six-membered pyran ring formed between C(3) and C(2’) [18].

2.3.4. Flavanones. Two flavanones, 198 and 199, were isolated from C. pulcherrimaL. in 2003 [47]. The third flavanone, liquiritigenin (200), was isolated in studies on thechemical constituents of C. millettii Hook [45].

2.3.5. Isoflavanones. Only two isoflavanones, 201 and 202, were isolated from C.pulcherrima cultured cells co-incubated with cork tissue [49].

2.4. Aromatic Phenols. C. sappan L. (Leguminosae) is distributed in Southeast Asia,it is called Su Mu in Chinese, and its dried heartwood, Sappan Lignum, is famous as ared dyestuff. Sappan Lignum is also used as herbal medicine against inflammation andimprovement of blood circulation. Many bioactive chemical components have beenisolated from this herb. Here, we present 25 compounds, 203– 227, from the plantSappan, and additional aromatic phenols, 228– 234, from the other plants of genusCaesalpinia. Brazilin (203), the main component of the Sappan Lignum, was firstmentioned in 1987. The relative configuration of 203 was established by synthetic,spectral, and chemical evidence. Compounds sappanol (179) and episappanol (182) areenantiomers from the Sappan Lignum, which have a highly similar structure as brazilin(203). When treated with a catalytic amount of acid, both of them underwent readily to203 with a new bond between C(4) and C(6’) [51]. Many compounds correlated to 203were isolated from the plant. 3’-O-Methylbrazilin (204), the 3’-MeO derivative ofbrazilin (203), was isolated from the Sappan Lignum [51]. Xie et al. isolated 203 andhematoxylin (205) from the MeOH extract of Sappan Lignum. The latter was almostidentical in structure to brazilin (203), except an additional OH group at C(8) [58].Brazilein (206), the oxidized product of 203, could be isolated in large quantities, whenthe organic extract was exposed to air and light [59]. It was also isolated from theoriginal plant [55].

Investigation of Sappan Lignum by Yang et al. afforded a new lactone namedbrazilide A (207), which is the first representative of a new skeleton type derived frombrazilin (203) [61]. Two novel compounds, 208 and 209, named caesalpins J and P,respectively, offer a new framework for the aromatic phenols of Sappan [63]. The twoantioxidant compounds 210 and 211 were isolated from C. sappan L. by multiple stepsof column chromatography and TLC, both compounds exhibited strong inhibition ofxanthine oxidase and the radical-scavenging activity [64]. From the MeOH extract ofVietnamese C. sappan, Nguyen et al. isolated seven compounds, 212– 215 and 217– 219,from this plant [52]. Compound 212, protosappanin A, was isolated in 2003, and itshowed moderate activity against Beauveria bassiana [62]. Compounds 213– 215, 220[55], and 221 [56] have the same C-skeleton as protosappanin A (212), except for thedifferent substituents at C(7).

Nagai and Nagumo isolated an inseparable mixture of two new dibenz[b,d]oxocinscombined with brazilin, named protosappanins E-1 and E-2 (216 and 217, resp.) from


Sappan Lignum, and separated them as isomeric hexamethyl ethers [65]. Chemical andspectral data of the hexamethyl ethers indicated that 216/217 might be transformed tobrazilin (203) and protosappanin B (214), on treatment with NaBH4 in alkali solutionvia brazilein (206) and protosappanin C (221) (Scheme 2) [65]. In 2005, protosappaninE-2 (217) was isolated as single component from this plant family and was identified forthe first time. Compound 217 can be formally split into two distinct groups based onanalysis 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 inScheme 3 [66].

A hypothetical biosynthetic relationship between sappanchalcone (178) andbrazilin (203), and that between brazilin-related compounds have been proposed.The tertiary carbinol C(6a) in 203 and C(7) in 178 derive from the common C-atomC(3) of the intermediate homoisoflavone A [65]. There were two routes for A to shift :a) the C-atom C(6’) attacks C(4) of A to form a new bond, and C(4)¼O disrupted toafford a new intermediate aldol B, which, through dehydration, is transformed tobrazilin (203). b) The C-atom C(6’) attacks C(4a) of A, which, upon isomerization givesthe intermediate C, which then transform via retro-aldol reaction to protosappanin C(221) or protosappanin A (212). All the progress was shown in Scheme 4 [65].


Scheme 2. Probable Degradation Mechanism of Compounds 216 and 217

Washiyama et al. isolated protosappanin D (222) from the Sappan Lignum withcompounds 212, 214, 217, and 221 [56]. Shu isolated two new dimers, 223 and 224, fromC. sappan, together with a stilbene, 225, and many compounds which were previouslymentioned [18]. (þ)-(8S,8’S)-Bisdihydrosiringenin (226) was isolated, together withthe new 3-benzylchroman 182 [55]. Bioassay-guided fractionation of a MeOH extractof Sappan Lignum provided the novel aromatic compound caesalpine J (227), whichwas 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 and231, but they did not show any biological activity [43]. Nozaki et al. isolated the uniquechalcone derivative 232 from the stems of C. ferrea Mart. The structure wasdetermined on the basis of 2D-NMR spectroscopy to be a chalcone trimer, linked by acyclobutane ring [68]. The new compound 233 was isolated from the C. decapetala forthe 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 isolatedfrom the air-dried leaves of C. pulcherrima and shown to be active against severalbacteria 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 chemicalconstituents of C. millettii afforded compounds 241– 246, and compounds 242 and 243were 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 thelong-chain compound 248 from the stem of C. decapetala [69]. Compounds 249 and 250were isolated from C. sappan in 2008 and 2009, respectively [54] [55].


Scheme 3. Possible Biogenetic Scheme for 219 from Caesalpin J (208)

2.6. Phenylpropanoids. Two coumarins, 251 and 252, and two lignanoids, 253 and254, 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 thetwo 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 atriterpene 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 isolatedhyperoside (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-


Scheme 4. Hypothetical Biosynthetic Relationship between Sappanchalcone 178 and 203, and the RelatedCompounds

dalis in 2000, with the same styrene skeleton but differing in the location of the OHgroup [73].

2.9. Peltogynoids. Only two peltogynoids, 268 and 269, were isolated from the stempart of C. pulcherrima, and their structures were deduced by their spectral data [46].

2.10. Anthraquinones. A benzoquinone, 270, and a naphthoquinone, 271, wereisolated 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 fromthe leaves of C. pulcherrima, and the latter was also found in the leaves of C. decapetalatogether 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]. Udenigweet 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].

3. Biological Activities. – 3.1. Cytotoxic Activity. Compound 80 was isolated in thefirst chemical study from the seeds of C. sappan [28] and demonstrated moderateinhibitory activity against KB cell line with an IC50 value of 4.4 mg/ml, but was inactiveagainst MCF-7 (breast adenocarcinoma), HeLa, and HT-29 cell lines (IC50 values of14.6, 19.0, and 14.0 mg/ml, resp.). Compounds 189 and 270, isolated from the stem of C.pulcherrima [20], were found to be cytotoxic in the KB test system in vitro, displayingED50 values of 2.8 and 3.2 mg/ml, respectively.

3.2. Antiproliferative Activity. Compounds 97, 98, and 101–103 were isolated fromdifferent parts of C. bonduc [25] [32]. Compounds 97 and 98 were found to inhibitMCF-7 breast cancer cell lines with IC50 values of 12.8 and 6.1 mm, respectively, alongwith the inhibition of endometrial and cervical cancer cell lines. Compounds 101– 103were tested for their antiproliferative activity against MCF-7, DU145 (prostatecarcinoma), C33A (cervical carcinoma), and Vero (African green monkey kidneyfibroblast) cancer cell lines, and were found to exhibit moderate-to-low IC50 (mm)values. Among the tested compounds, 102 was found to show a better activity profileagainst cervical and prostate, and breast carcinoma cell lines. Pauferrol A (232) wasisolated from the stems of C. ferrea [68] and showed potent inhibitory activity againsthuman topoisomerase II, with an IC50 value of 2.1 mm, and cell proliferation inhibitoryactivity through the induction of apoptosis in human leukemia HL60 cells, with an IC50

value of 5.2 mm.3.3. Antimicrobial Activity. Compounds 30– 33 and 235 were isolated from the air-

dried leaves of C. pulcherrima [24] and tested for their antimicrobial potential. Theresults obtained indicated that 30 and 32 exhibited moderate activities against S. aureus,while 31, 33, and 235 showed only weak activities. Furthermore, except for 33, all thosetested had moderate activity against C. albicans. Compound 235 was the most activeamong the tested compounds against T. mentagrophytes, but with lower activity thanthe standard antifungal agent, chlortrimazole.

Oleanolic acid (156) was found active against Bacillus subtilis, and both methicillin-sensitive and -resistant Staphylococcus aureus with MIC values of 8 (17.5 mm), 8 and 64(140 mm) mg/ml, respectively [43]. Compounds 236– 239 were tested for their activity to


intensify the susceptibility of methicillin-resistant Staphylococcus aureus to oxacillin ata dose of 25 mg/ml in 22 strains. Compound 237 displayed the strongest activity with themean inhibitory concentration of oxacillin at 4 mg/ml, while the concentration for 239was 32 mg/ml; the others hardly showed any effect [70]. Compound 271 exhibited astrong inhibition at 5 and 2 mg/disk, and moderate inhibition at 1, 0.5, and 0.25 mg/diskin the test with Clostridium perfringens, whereas its growth inhibition activity againstLactobacillus casei at 5 and 2 mg/disk was weak. Compared to the naphthoquinonederivatives, the structure�activity relationship study revealed that compound 271 had aselective growth inhibition activity against Clostridium perfringens and could be apotent drug against diseases caused by Clostridium perfringens [74].

3.4. Antimalarial Activity. Compounds 4, 42 –47, 58, 119, 122, 123, and 137– 140exhibited significant dose-dependent inhibitory effects on Plasmodium falciparumFCR-3/A2 growth in vitro. Their IC50 values ranged from 90 nm to 6.5 mm, andcompound 140 showed the most potent inhibitory activity (IC50 90 nm) [6].

3.5. Immunosuppressive and Anti-Inflammatory Activity. Compounds 164, 165, 191,198, and 199, isolated from the aerial part of C. pulcherrima, were studied inlipopolysaccharide (LPS)- and interferon (IFN)-g activated murine peritoneal macro-phages. All of the compounds significantly and dose-dependently inhibited theinflammatory mediators nitric oxide (NO) and cytokines (tumor necrosis factor(TNF)-a and interleukin (IL)-12) [48]. The study supports the use of C. pulcherrimafor the treatment of inflammatory diseases in traditional medicine. Compounds 178,203, 212, 214, 216/217, 221, and 222, isolated from the Sappan Lignum were evaluatedfor their inhibitory effects on several inflammatory mediators, with the result thatcompound 203 inhibited NO production and showed almost no inhibition in PGE2,while compound 178, 216/217, and 222 inhibited both NO and PGE2 production, andsuppressed TNF-a, IL-6, COX-2, and iNOS mRNA expression [56]. Compound 212was tested in heart allograft operation assay together with cyclosporine. The resultsshowed that compound 212 or cyclosporine significantly prolonged heart allograftsurvival, alleviated myocardial pathologic damages, decreased the CD4þ/CD8þ cellratio, and inhibited perforin and granzyme B mRNA expressions in the graft [76].Brazilein (206) and the EtOH extract of C. sappan could distinctly inhibit theproliferation of T lymphocyte stimulated by concanavalin A (Con A), and theproliferation of B lymphocyte stimulated by lipopolysaccharides (LPS), and 206 couldsuppress mice humoral immune response by plaque forming cell (PFC) test [59].

3.6. Antiviral Activity. Compounds 25– 28, 120, and 158 were evaluated for theireffects on the proliferation of the Para3 virus, and 25 – 28 and 120 showed significantactivities against the Para3 virus, with IC50 values ranging between 7.8 and 14.8 mg/ml.However, compound 120, which is the only furanoditerpenoid lactone, is highly toxic,with a TI value of 3.0. It is noteworthy that the TI value of compound 25 is almost thesame as that of ribavirin, which serves as a positive control in the bioassay. Compound158 shows moderate activity against the Para3 virus [22]. In the bioassay, compound121 exhibited inhibitory activity against the RSV with IC50 of 24.2 mg/ml, TC50 of138.3 mg/ml, and SI of 5.7 in cell culture, the selectivity index, SI>4 for naturalproducts is considered significant. However, unlike other furanoditerpenoids, 121 wasinactive against the para-3 and the Flu-A virus [75].


4. Conclusions. – Plants of the genus Caesalpinia are widely distributed all over theworld, and many species of this genus have been used as traditional herbal medicines.Compounds isolated from the genus display powerful biological activities and havepotency to be new defensive agents against several kinds of diseases. However,questions arose concerning the structure�activity relationships and elucidation of theaction mechanism, since compounds belonging to the same skeleton type displayeddifferent levels of activity against the same antigen. Further studies to explore themechanism at the molecular level and to exploit other types of constituents arenecessary.

We are grateful for the financially supports from the Scientific Research Foundation for the ReturnedOverseas Chinese Scholars of Hebei Province (2006-02) and the Scientific Research Foundation of HebeiProvince (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), andgrant-in-aid from the Japan Society for the Promotion of Science (No. 22580112) for the financial support.

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Received June 18, 2010


Chemical Constituents of Plants from the Genus Caesalpinia

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