Limonoids are modified tetranortriterpenoids, classified on the basis of which of the four rings (A, B, C and D) in the intact triterpene nucleus have been oxidized. The order Rutales produces a variety of seco-limonoids, such as A, B, C, D, AB, AD, and BD-ring seco-limonoids. The Meliaceae family, belonging to the order Rutales, has yielded several D-ring and B, D-ring seco-limonoids This review describes the occurrence, biosynthesis, biological activity and NMR spectroscopy of D ring seco-limonoids, such as gedunin derivatives and B, D-ring seco-limonoids, such as methyl angolensates, xyloccensins, methyl meliacates, phragmalins and modified phragmalins. The literature from 1990 to 2005 is reviewed.
NewtonAC, BakerP, RamnarineS, MesenJF, LeakeyRRB. (1993) The mahogany shoot borer - prospects for control. Forest Ecology and Management, 57, 301–328.
2.
ChampagneDE, KoulO, IsmanMB, ScudderGGE, TowersGHN. (1992) Biological activity of limonoids from the Rutales. Phytochemistry, 31, 377–394.
3.
KrausW, GrimmingerW, SawitzkiG. (1978) Toonacilin and 6-acetoxytoonacilin, Two novel B-seco-tetranortriterpenoids with antifeeding activity. Angewandte Chemie International Edition English, 17, 452–453.
4.
PowellRG, MikolajczakKL, ZilkowskiBW, MantusEK, CherryD, ClardyJ. (1991) Limonoid antifeedantants from seed of Sandoricum koetjape. Journal of Natural Products, 54, 241–246.
MordueAJ, SimmondsMSJ, LeySV, BlaneyWM, MordueW, NasiruddinM, NisbetAJ. (1998) Actions of azadirachtin, a plant. allelochemical, against insects. Pesticide Science, 54, 277–284.
7.
ChampagneDE, IsmanMB, TowersGHN. (1989) In Insecticides of Plant Origin, ArnasonTJ, PhilogeneBJR, MorandP. (Eds). American Chemical Society, Washington DC, 95–109.
8.
KoulO, IsmanMB. (1992) Toxicity of the limonoid allelochemical cedrelone to noctuid larvae. Entomologia Experimentalis et Applicata, 64, 281–287.
9.
ZhouH, HamazakiA, FontanaJD, TakahashiH, WandescheerCB, FukuyamaY. (2005) Cytotoxic limonoids from Brazilian Melia azaderachta. Chemical and Pharmaceutical Bulletin, 53, 1362–1365.
DarzielJM. (1937) The Useful Plants of West Tropical Africa, Crown Agents for the Colonies, London, p. 325.
12.
MacKinnonS, DurstT, ArnasonJT, AngerhoferC, PezzutoJ, Sanchet-VindasPE, PovedaLJ, GbeassorM. (1997) Antimalarial activity of tropical Meliaceae extracts and gedunin derivatives. Journal of Natural Products, 60, 336–341.
13.
SiddiquiS, FaiziS, SiddiquiBS, Ghiassudin (1992) Constituents of Azadirachta indica: Isolation and structure elucidation of a new antibacterial tetranortriterpenoid, mahmoodin and a new protolimonoid, naheedin. Journal of Natural Products, 19, 303–310.
BevanCWL, EkongDEU, TaylorDAH. (1965) Extractives from West African members of the family Meliaceae. Nature (London), 206, 1323–1325.
16.
AdesoganEK, OkorieDA, TaylorDAH. (1970) Limonoids from Khaya anthotheca. Journal of the Chemical Society C, 205–210.
17.
NakataniM. (2001) Bioactive Compounds from Natural Sources (Tringali, C. ed.), Taylor and Francis, London and New York.
18.
TaylorDAH. (1969) Limonoids from Khaya nyasica. Journal of the Chemical Society C, 2439–2442.
19.
WhiteF, StylesBT. (1963) In ‘Flora Zambesiaca’, Crown Agents, II (1), p. 289.
20.
TaylorDAH. (1967) Nyasin, an extractive from Khaya nyasica. Chemical Communications, 500.
21.
BevanCWL, HalsallTG, NwajiMN, TaylorDAH. (1962) West African timbers. Part V. The structure of khivorin, a constituent of Khaya ivorensis. Journal of the Chemical Society, 768–770.
22.
TaylorDAH. (1968) 11β-Acetoxykhivorin, a new limonoid. Chemical Communications, 1172.
23.
TaylorDAH. (1970) Limonoids from Khaya madagascariensis. Journal of the Chemical Society C, 336–339.
24.
BaldwinMA, LoudonAG, MaccollA, BevanCWL. (1967) The mass spectra of meliacins and related compounds. Part I. Gedunin and related compounds. Journal of the Chemical Society C, 1026–1034.
25.
BevanCWL, PowellJW, TaylorDAH. (1963) West African timbers. Part VI. Petroleum extracts from species of the genera Khaya, Guarea, Carapa, and Cedrela. Journal of the Chemical Society, 980–982.
26.
AdesoganEK, PowellJW, TaylorDAH. (1967) Extractives from the seed of Khaya senegalensis. Journal of the Chemical Society C, 554–555.
27.
AkisanyaA, AreneEO, BevanCWL, EkongDEU, NwajiMN, OkogunJI, PowellJW, TaylorDAH. (1966) West African timbers. Part XII. The inter-relation of gedunin and khivorinJournal of the Chemical Society C, 506–508.
28.
TaylorDAH. (1977) 13C-Nuclear magnetic resonance spectroscopy of some limonoids, Part–II. The spectra of a series of meliacolide derivatives. Journal of Chemical Research Synopsis, 2.
29.
HouslyJR, KingFE, KingTJ, TaylorPR. (1962) The chemistry of hardwood extractives. Part XXXIV. Constituents of Guarea species. Journal of the Chemical Society, 5095–5103.
OhochukuNS, TaylorDAH. (1970) 6β-Hydroxygedunin. Journal of the Chemical Society C, 421–422.
32.
BurkeBA, ChanWR, MagnusKE, TaylorDR. (1969) Extractives of Cedrela odorata L-III: The structure of photogedunin. Tetrahedron, 25, 5007–5011.
33.
PaulaJRD, VieiraIJC, Da SilvaMFGF, FilhoER, FernandesJB, VieiraPC, PinheiroAL, VilelaEF. (1997) Sesquiterpenes, triterpenoids, limonoids and flavonoids of Cedrela odorata graft and speculations on the induced resistance against Hypsipyla grandella. Phytochemistry, 44, 1449–1454.
34.
SiddiquiS, FaiziS, SiddiquiBS. (1984). Studies on the chemical constituents of Azadirachta indica-Part-I: Isolation and characterization of a new tetranortriterpenoid, nimolicinol. Heterocycles, 22, 295–298.
35.
HallurG, KrishnaAS, BhatSV. (2002) Three new tetranortriterpenoids from neem seed oil. Journal of Natural Products, 65, 1177–1179.
ChatterjeeA, KunduB, ChakraborthyT, ChandrasekharanS. (1970) Extractives of Aphanamixis polystachya Wall: The structures and stereochemistry of aphanamixin and aphanamixinin. Tetrahedron, 26, 1859–1867.
38.
KadotaS, MarpaungL, KikuchiT, EkimotoH. (1990) Constituents of the seeds of Swietenia mahagoni III. Structure of mahonin and secomahoganin. Chemical and Pharmaceutical Bulletin, 38, 1495–1500.
39.
NakataniM, AbdelgaleilSAM, KassemSMI, TakezakiK, OkamuraH, IwagawaT, DoeM. (2002) Three new modified limonoids from Khaya senegalensis. Journal of Natural Products, 65, 1219–1221.
40.
AdesoganEK, TaylorDAH. (1968) Extractives from Khaya senegalensis. Journal of the Chemical Society C, 1974–1981.
41.
ConnollyJD, Mc CrindleR, OvertonKH, WarnockWDC. (1967) Tetranortriterpenoids-III: 6-Hydroxy- and 6-acetoxy- methyl angolensate from the heartwood of Khaya grandifoliola. Tetrahedron, 23, 4035–4039.
42.
ChanW. R, MagnusE, MootooBS. (1967) Extractives from Cedrela odorata L. The structure of methyl angolensate. Journal of the Chemical Society C, 171–177.
43.
ConnollyJD, OkorieDA, TaylorDAH. (1972) Limonoid extractives from species of Guarea. An unusual shielding effect on an acetyl group. Journal of the Chemical Society Perkin Transactions1, 1145–1146.
TaylorDAH. (1981) Ekebergin, a limonoid extractive from Ekebergia capensis. Phytochemistry, 20, 2263–2265.
46.
TaylorARH, TaylorDAH. (1984) Limonoids from Ekebergia pterophylla Phytochemistry, 23, 2676–2677.
47.
ConnollyJD, MacLellanM. (1976) Limonoids from Xylocarpus moluccensis. Journal of the Chemical Society Perkin Transactions I, 1993–1995.
48.
AlviKA, CrewsP, AalbersbergB, PrasadR. (1991) Limonoids from the Fijian medicinal plant dabi (Xylocarpus). Tetrahedron, 47, 8943–8948.
49.
JunW, ZhangS, QiangX, QingxinL, JiansheH, LijuanL, LianminH. (2004). Xyloccensin L, a novel limonoid from Xylocarpus granatum. Tetrahedron Letters, 45, 591–593.
50.
JunW, ZhangS, QiangX, QingxinL, JiansheH, ZhihuiX, LijunanL. (2003) Xyloccensin M and N, two new B, D-seco limonoids from Xylocarpus granatum. Zeitschrift fuer Naturforschung, 58B, 1216–1218.
51.
WattJM, Breyer-BrandwijkMG. (1962) The Medicinal and Poisonous Plants of Southern and Eastern Africa, E and L. Livingstone Ltd, London, 469.
52.
NakataniM, AbdelgaleilSAM, KurawakiJ, OkamuraH, IwagawaT, DoeM. (2001) Antifeedant rings B and D opened limonoids from Khaya senegalensis. Journal of Natural Products, 64, 1261–1264; (2000) Seneganolide, a novel antifeeding mexicanolide from Khaya senegalensis. Chemistry Letters, 876–877.
53.
AbdelgaleilSAM, OkamuraH, IwagawaT, DoeM, NakataniM. (2000) Novel rings B, D-secolimonoids from the stem bark of Khaya senegalensis. Heterocycles, 53, 2233–2240.
54.
TchimeneMK, TaneP, NgamgaD, ConnollyJD, FarrugiaLJ. (2005) Four tetranortriterpenoids from the stem bark of Khaya anthotheca. Phytochemistry, 66, 1088–1093.
55.
FerreiraICP, CortezDAG, Da SilvaMFGF, FoER, VieiraPC, FernandesJ. (2005) Acylperoxylated and seco-mexicanolides from stems of Khaya anthotheca. Journal of Natural Products, 68, 413–416.
56.
ConnollyJD, HendersonR, McCrindleR, OvertonKH, BhaccaNS. (1965) Tetranortriterpenoids. Part I. [Bicyclononanolides. Part I.] The constitution of swietenine. Journal of the Chemical Society, 6935–6948.
ChakrabartyT, ChatterjeeA. (1955) On the constitution of swietenine: The non-bitter principle of the seeds of Swietenia macrophylla. Journal of the Indian Chemical Society, 32, 179–186.
59.
ChakrabartyT, ChatterjeeA. (1957) The constitution of swietenine, the non-bitter principles of the seeds of Swietenia macrophylla Part II. Journal of the Indian Chemical Society, 34, 117–120.
60.
ChanKC, TangTS, TohHT. (1976) Isolation of swietenolide diacetate from Swietenia macrophylla. Phytochemistry, 15, 429–430.
61.
SircarSSG, ChakrabartyT. (1951) The chemical investigation of the seeds of Swietenia macrophylla Part-I: The non-bitter principle. Journal of the Indian Chemical Society, 28, 207–210.
62.
CoombesPH, MulhollandDA, RandrianarivelojosiaM. (2005) Mexicanolide limonoids from the Madagascan Meliaceae Quivisia papinae. Phytochemistry, 66, 1100–1107.
KadotaS, MarpaungL, KikuchiT, EkimotoH. (1989) Mahonin and secomahoganin, new tetranortriterpenoids from Swietenia mahogani. Chemical and Pharmaceutical Bulletin, 37, 1419–1421.
70.
KadotaS, MarpaungL, KikuchiT, EkimotoH. (1989) Antagonists of platelet activating factor from Swietenia mahogani. Tetrahedron Letters, 30, 1111–1114.
71.
KadotaS, MarpaungL, KikuchiT, EkimotoH. (1990) Constituents of the seeds of Swietenia mahogani I. Isolation, structures, and 1H and 13C-nuclear magnetic resonance signal assignments of new tetranortriterpenoids related to swietenin and swietenolide. Chemical and Pharmaceutical Bulletin, 38, 639–651.
72.
KadotaS, MarpaungL, KikuchiT, EkimotoH. (1990) Constituents of the seeds of Swietenia mahogani II. Structures of swietemahonins A, B, C, D, E, F and G and swietemahonalide. Chemical and Pharmaceutical Bulletin, 38, 894–901.
73.
SondengamB, KamgaCS, ConnollyJD. (1980) Proceranolide, a novel tetranortriterpenoid from Carapa procera. Phytochemistry, 19, 2488.
74.
KadataS, YnagawaK, KikuchiT, TanakaK. (1990) Mahagonin, a novel dimeric tetranortriterpenoid from Swietenia mahogani. Tetrahedron Letters, 31, 5943–5946.
75.
BaldwinSM, AliA, MotilalR, PingalR, RamlalA, KhanAyub, ReynoldsWF, McLeanS. (1999) Limonoids from Swietenia macrophylla and S. aubrevilleana. Journal of Natural Products, 62, 1514–1517.
76.
StylesBT. (1981) Swietenioideae. In: Flora Neotropica, PenningtonTD, StylesBT, TaylorDAH. (Eds). New York Botanical Garden, New York, Monograph No. 28, Meliaceae, pp. 359–418.
77.
StandleyPC. “Trees and Shrubs of Mexico”, United States National Herbarium, Washington DC, 1920–1926, p. 560.
78.
MartinezM. (1989) “Las Plantas Medicinales de Mexico”, Ediciones Botas, Mexico D.F., 6th edition, p. 390.
79.
Soto-NunezJC. (1987) “Las Plantas Medicinales ysu Uso Tradicional en la Cuenca del Rio Balsas: Estados de Michoacan y Guerrero, Mexico”, B.S. Thesis, Facultad de Ciencias, Universidad Nacional Autonoma de Mexico, Mexico DF, p. 98.
80.
DiazJL. (1976) Uso de la Plantas Medicinales de Mexico, “Monografias Cientificas II, IMEPLAM, Mexico DF, p. 116.
81.
CorreaRS, MataR, AnayaAL, BautistaBH, VillenaR, GarciaMS, ByeR, LinaresE. (1993) New tetranortriterpenoids from Swietenia humilis. Journal of Natural Products, 56, 1567–1574.
82.
VillarrealAJC, ToscanoRA, CookM, ArnasonJT, ByeR, MataR. (1998) Limonoids from Swietenia humilis and Guarea grandiflora (Meliaceae). Phytochemistry, 40, 1981–1988.
83.
PerusquiaM, HernandezRH, JimenezMA, MirandaRP, MataR. (1997) Contractile response induced by a limonoid (humilinolide A) on spontaneous activity of isolated smooth muscle. Phytotherapy Research, 11, 354–357.
84.
AbdelgaleilSAM, IwagawaT, DoeM, NakataniM. (2004) Antifungal limonoids from the fruits of Khaya senegalensis. Fitoterapia, 75, 566–572.
85.
KokpolU, ChawasiriW, Tip-pyangS, VeerachatoG, ZhaoF, SimpsonJ, WeaversRT. (1996) A limonoid from Xylocarpus granatum. Phytochemistry, 41, 903–905.
86.
VeitchNC, WrightGA, StevensonPC. (1999) Four new tetranortriterpenoids from Cedrela odorata associated with leaf rejection by Exopthalmus jekelianus. Journal of Natural Products, 62, 1260–1263.
87.
DalzielJM. (1937) In: The useful plants of West Tropical Africa: Crown Agents for the Colonies: London, p. 325.
88.
MonaMGS, IwagawaT, DoeM, NakataniM. (2003) Swietenialides, novel ring-D opened phragmalin limonoid orthoesters from Swietenia mahogany. Tetrahedron, 59, 8027–8033.
89.
CoombesPH, MulhollandDA, RandrianarivelojosiaM. (2003) Phragmalin limonoids from the Madagascan Meliaceae Neobeguea leandreana. Journal of Natural Products, 66, 735–738.
90.
GopalRM, MuralikrishnaE, ConnollyJD. (1985) Three tetranortriterpenoids from fruits of Soymida febrifuga. Phytochemistry, 24, 305–307.
91.
RandrianarivelojosiaM, KotsosMP, MulhollandDA. (1999) A limonoid from Neobeguea mahafalensis. Phytochemistry, 52, 1141–1143.
RegettliVT, ChristophT. (1978) Die Chukrasine A, B, C, D und E, fünf neue Tetranortriterpene aus Chukrasia tabularis. Helvetica Chimica Acta, 61, 1814–1831.
94.
JunW, QiangX, JiansheH, ZhihuiX, ShuhnaQ, QingxinL, ZhangS. (2004) Xyloccensins O and P, unique 8, 9, 30-phragmalin ortho esters from Xylocarpus granatum. Organic Letters, 6, 1841–1844.
95.
CuiJ, DengZ, LiJ, FuH, ProkschP, LinW. (2005) Phragmalin-type limonoids from the mangrove plant Xylocarpus granatum. Phytochemistry, 66, 2334–2339.
OlmoLRV, Da SilvaMFGF, FilhoER, VieiraPC, FernandesJB, MarsaioliAJ, PinheiroA, VilelaEF. (1996) Rearranged limonoids from Khaya senegalensis. Phytochemistry, 42, 831–837; (1997) Limonoids from leaves of Khaya senegalensis. Phytochemistry, 44, 1157–1161.
98.
TehuendemMHK, AyaforJF, ConnollyJD, SternerO. (1998) Khayalactone, a novel limonoid from Khaya grandifoliola. Tetrahedron Letters, 39, 719–722.
99.
MulhollandDA, TaylorDAH. (1992) Limonoids from Australian members of the Meliaceae Phytochemistry, 31, 4163–4166. and TaylorDAH (1983) Limonoid extractives from Xylocarpus moluccensis. Phytochemistry, 22, 1297–1299.
100.
TcouankeuJC, TsamoE, SondengamBL (1990) Entilins A and B, two novel heptanortriterpenoid derivatives from Entandrophragma utile (Meliaceae): Structural elucidation using 2D-NMR long-range δC/δH correlation experiments. Tetrahedron Letters, 31, 4505–4508.
101.
CucaSuarez LE, MenichinaF, MonacheFD. (2002) Tetranortriterpenoids and dihydrocinnamic acid derivatives from Hortia colombiana. Journal of Brazilian Chemical Society, 13, 339–344.
102.
BennR, GuntherH. (1983) Modern pulse methods in high-resolution NMR spectroscopy. Angewandte Chemie International Edition (English), 22, 350–380.
103.
SandersJKM, HunterBK. (1993) Modern NMR Spectroscopy, 2nd Ed. Oxford University Press, Oxford.
104.
DeromeAE. (1987) Modern NMR Techniques for Chemistry Research, Pergamon Press, Oxford.
105.
FriebolinHP. (1993) Basic One and Two dimensional NMR spectroscopy, 2nd Ed. VCH, Weinhein.
106.
DuddeckH, DietrichW, TothG. (1998) Structure Elucidation by Modern NMR, A Work Book. 3rd Ed. Darmstandt; Steinkoptf, New York; Springer.
107.
GuntherH. (1992) NMR Spectroskopie, Thieme, Stuttgart, New York; GuntherH. (1995) NMR Spectroscopy Basic Principles, Concepts and Application in Chemistry, 2nd Ed. Wiley, New York.
108.
GriesingerC, SchwalbeH, SchleucherJ, SattlerM. (1994) In Two dimensional NMR Spectroscopy, Applications for Chemists and Biochemists. CroasmunWR, CarlsonRMK, eds) 2nd Ed. VCH, New York.
