Momilactone B: Difference between revisions
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| verifiedrevid = 431520650 |
| verifiedrevid = 431520650 |
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| ImageFile = Momilactone B.svg |
| ImageFile = Momilactone B.svg |
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| ImageSize = |
| ImageSize = |
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| IUPACName = |
| IUPACName = (3''S''-(3α,3β,5aβ,8α,10aα,10bβ,10cβ))-8-Ethenyl-3a,5a,7,8,9,10,10a,10c-octahydro-3a,8-dimethyl-,4''H''-3,10b-ethano-1''H'',3''H''-benzo[''f'']furo[4,3,2-''de'']-2-benzopyran-4-one |
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| OtherNames = |
| OtherNames = |
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|Section1={{Chembox Identifiers |
|Section1={{Chembox Identifiers |
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| CASNo_Ref = {{cascite|changed|??}} |
| CASNo_Ref = {{cascite|changed|??}} |
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| CASNo = 51415-08-8 |
| CASNo = 51415-08-8 |
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| PubChem = |
| PubChem = 3084979 |
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| ChemSpiderID = 9755519 |
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| ChEMBL = 2271028 |
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| StdInChI=1S/C20H26O4/c1-4-17(2)6-5-13-12(10-17)9-14-15-18(3,16(21)24-14)20(22)8-7-19(13,15)11-23-20/h4,9,13-15,22H,1,5-8,10-11H2,2-3H3/t13-,14?,15+,17-,18+,19+,20?/m1/s1 |
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| StdInChIKey = SONPFFIKLYCKOY-WXVXRDCTSA-N |
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| SMILES = C[C@]1(CC[C@@H]2C(=CC3[C@@H]4[C@]25CCC([C@@]4(C(=O)O3)C)(OC5)O)C1)C=C |
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|Section2={{Chembox Properties |
|Section2={{Chembox Properties |
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| C=20 | H=26 | O=4 |
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| Formula = C<sub>20</sub>H<sub>26</sub>O<sub>4</sub> |
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| MolarMass = 330.4180 g/mol |
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| Appearance = |
| Appearance = |
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| Density = |
| Density = |
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| MeltingPtC = 242 |
| MeltingPtC = 242 |
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| MeltingPt_notes = (decomp) |
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'''Momilactone B''' is an [[allelopathic]] agent produced from the roots of rice ([[Oryza sativa|''Oryza sativa'' L.]]) (100 mg from 200 kg dry rice husk).<ref name=momilactone_B_isolation>{{cite journal |author1=Kato, T. |author2=Kabuto, C. |author3=Sasaki, N. |author4=Tsunagawa, M. |author5=Aizawa, H. |author6=Fujita, K. |author7=Kato, Y. |author8=Kitahara, Y. |title=Momilactones, Growth Inhibitors from Rice, Oryza Sativa L. | journal= |
'''Momilactone B''' is an [[allelopathic]] agent produced from the roots of rice ([[Oryza sativa|''Oryza sativa'' L.]]) (100 mg from 200 kg dry rice husk).<ref name=momilactone_B_isolation>{{cite journal |author1=Kato, T. |author2=Kabuto, C. |author3=Sasaki, N. |author4=Tsunagawa, M. |author5=Aizawa, H. |author6=Fujita, K. |author7=Kato, Y. |author8=Kitahara, Y. |title=Momilactones, Growth Inhibitors from Rice, Oryza Sativa L. | journal=Tetrahedron Lett. | year=1973 | volume=14 | issue=39 | pages=3861–3864 | doi= 10.1016/S0040-4039(01)87058-1}}</ref> It has been shown to be produced in high concentrations by the roots of rice seedlings.<ref name=production_paper>{{cite journal |author1=Toyomasu, T. |author2=Kagahara, T. |author3=Okada, K. |author4=Koga, J. |author5=Hasegawa, M. |author6=Mitsuhashi, W. |author7=Sassa, T. |author8=Yamane, H. |title=Diterpene Phytoalexins are Biosynthesized in and Exuded from the Roots of Rice Seedlings | journal=Biosci. Biotechnol. Biochem. | year=2008 | volume=72 | issue=2 | pages=562–567 | doi= 10.1271/bbb.70677 | pmid=18256463|doi-access=free }}</ref> The production of momilactone B has also been induced in response to infection by [[Magnaporthe grisea|blast fungus]] (''[[Magnaporthe grisea|Pyricularia oryzae]]'') or irradiated with [[Ultraviolet|UV light]].<ref name=momilactone_B_induced_production>{{cite journal |author1=Cartwright, D. W. |author2=Langcake, P. |author3=Pryce, R. J. |author4=Leworthy, D. P. |author5=Ride, J. P. |title=Isolation and Characterization of Two Phytoalexins from Rice as Momilactones A and B | journal=Phytochemistry | year=1981 | volume=20 | issue=3 | pages=535–537 | doi= 10.1016/S0031-9422(00)84189-8|bibcode=1981PChem..20..535C }}</ref> More recently it has been shown to be a potential [[Chemotherapy|chemotherapeutic agent]] against [[Colorectal cancer|human colon cancer]].<ref name=cytotoxic_activity>{{cite journal |author1=Kim, S. |author2=Park, H. |author3=Park, E. |author4=Lee, S. |title=Cytotoxic and Antitumor Activity of Momilactone B from Rice Hulls | journal=J. Agric. Food Chem. | year=2007 | volume=55 | issue=5 | pages=1702–1706 | doi= 10.1021/jf062020b | pmid=17326606}}</ref> |
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__TOC__ |
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==Biosynthesis== |
==Biosynthesis== |
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Of the |
Of the 15 [[phytoalexins]] that have been isolated from rice, 14, including momilactone B, are [[Terpene|diterpenes]] commonly [[Biosynthesis|biosynthesized]] from [[geranylgeranyl diphosphate]] (GGDP). Research on the synthetic pathway for momilactone B has found it involves a set of enzymes that are encoded by genes located on chromosome 4.{{cn|date=March 2023}} |
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The first step in the [[biosynthesis]] of momilactone B is the [[Cyclic compound|cyclization]] of [[Geranylgeranyl pyrophosphate|GGDP]] to ''syn''-copalyl diphosphate (''syn''-CDP), a type B{{ |
The first step in the [[biosynthesis]] of momilactone B is the [[Cyclic compound|cyclization]] of [[Geranylgeranyl pyrophosphate|GGDP]] to ''syn''-copalyl diphosphate (''syn''-CDP), a type B{{clarify|date=January 2017}} [[Cyclic compound|cyclization]]. This is initiated by the addition of a [[proton]] to the terminal [[Alkene|olefin]] bond of [[Geranylgeranyl pyrophosphate|GGDP]]. The [[genes]] encoding for ''syn''-CDP [[synthase]] was found by Otomo ''et al.''. in 2004.<ref name=Type_B_Cyclase>{{cite journal |author1=Otomo, K. |author2=Kenmoku, H. |author3=Oikawa, H. |author4=König, W. A. |author5=Toshima, H. |author6=Mitsuhashi, W. |author7=Yamane, H. |author8=Sassa, T. |author9=Toyomasu, T. |title=Biological functions of ''ent''- and ''syn''-copalyl diphosphate synthases in rice: key enzymes for the branch point of gibberellin and phytoalexin biosynthesis | journal=Plant J. | year=2004 | volume=39 | issue=6 | pages=886–893 | doi= 10.1111/j.1365-313X.2004.02175.x | pmid=15341631|doi-access=free }}</ref> This was labeled as ''OsCyc''1 (''Oryza sativa Cyclase'' 1). According to the rice genome database, ''OsCyc1'' corresponds to ''OsCPS''4 (AL662933) found in chromosome 4 (14.3cM) discovered by Sakamoto ''et al.''. in 2004.<ref name=Gene_correspondence>{{cite journal | doi=10.1104/pp.103.033696 |author1=Sakamoto, T. |author2=Miura, K. |author3=Itoh, H. |author4=Tatsumi, T. |author5=Ueguchi-Tanaka, M. |author6=Ishiyama, K. |author7=Kobayashi, M. |author8=Agrawal, G. K. |author9=Takeda, S. |author10=Abe, K. |author11=Miyao, A. |author12=Hirochika, H. |author13=Kitano, H. |author14=Ashikari, M. |author15=Matsuoka, M. |title=An Overview of Gibberellin Metabolism Enzyme Genes and Their Related Mutants in Rice | journal=Plant Physiol. | year=2004 | volume=134 | issue=4 | pages=1642–1653 | pmid=15075394 | pmc=419838}}</ref> |
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The second step is the cyclization of ''syn''-CDP to 9β-pimara-7,15-diene. This step is initiated by the [[Elimination reaction|elimination]] of the [[diphosphate|diphosphate group]], a type A{{ |
The second step is the cyclization of ''syn''-CDP to 9β-pimara-7,15-diene. This step is initiated by the [[Elimination reaction|elimination]] of the [[diphosphate|diphosphate group]], a type A{{clarify|date=January 2017}} [[cyclization]]. The [[genes]] encoding for the type A [[Adenylyl cyclase|cyclase]] were found by Otomo ''et al.''. in 2004.<ref name=Type_A_Cyclase>{{cite journal |author1=Otomo, K. |author2=Kanno, Y. |author3=Motegi, A. |author4=Kenmoku, H. |author5=Yamane, H. |author6=Mitsuhashi, W. |author7=Oikawa, H. |author8=Toshima, H. |author9=Itoh, H. |author10=Matsuoka, M. |author11=Sassa, T. |author12=Toyomasu, T. |title=Diterpene Cyclases Responsible for the Biosynthesis of Phytoalexins, Momilactones A, B, and Oryzalexins A-F in Rice | journal=Biosci. Biotechnol. Biochem. | year=2004 | volume=68 | issue=9 | pages=2001–2006 | doi= 10.1271/bbb.68.2001 | pmid=15388982|s2cid=9892116 |doi-access=free }}</ref> It is suggested that ''OsKS''4, located on chromosome 4 (14.3cM) is one of the [[genes]] responsible for [[phytoalexin]] biosynthesis. After [[UV-radiation]], ''OsKS''4 mRNA levels rise drastically in response to the attack. |
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[[Image:Type A Cyclase.png|center|600px| |
[[Image:Type A Cyclase.png|center|600px|''syn''-CDP cyclization to 9β-pimara-7,15-diene]] |
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Further [[oxidation]] of the 9β-pimara-7,15-diene compound followed by [[lactone]] and [[lactol]] formation yields momilactone B. Though the [[gene sequence]] of these [[oxidation]]s is unknown, [[P450|P450 monooxygenase genes]] have been identified near the cyclase [[genes]] on |
Further [[oxidation]] of the 9β-pimara-7,15-diene compound followed by [[lactone]] and [[lactol]] formation yields momilactone B. Though the [[gene sequence]] of these [[oxidation]]s is unknown, [[P450|P450 monooxygenase genes]] have been identified near the cyclase [[genes]] on chromosome 4. |
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[[Image:Oxidation to Momilactone B.png|center|600px| |
[[Image:Oxidation to Momilactone B.png|center|600px|Oxidation of 9β-pimara-7,15-diene to Momilactone B]] |
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== Stereochemistry == |
== Stereochemistry == |
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Latest revision as of 09:34, 17 November 2023
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| Names | |
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| IUPAC name
(3S-(3α,3β,5aβ,8α,10aα,10bβ,10cβ))-8-Ethenyl-3a,5a,7,8,9,10,10a,10c-octahydro-3a,8-dimethyl-,4H-3,10b-ethano-1H,3H-benzo[f]furo[4,3,2-de]-2-benzopyran-4-one
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| Identifiers | |
3D model (JSmol)
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| ChEMBL | |
| ChemSpider | |
PubChem CID
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CompTox Dashboard (EPA)
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| Properties | |
| C20H26O4 | |
| Molar mass | 330.424 g·mol−1 |
| Melting point | 242 °C (468 °F; 515 K) (decomp) |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Momilactone B is an allelopathic agent produced from the roots of rice (Oryza sativa L.) (100 mg from 200 kg dry rice husk).[1] It has been shown to be produced in high concentrations by the roots of rice seedlings.[2] The production of momilactone B has also been induced in response to infection by blast fungus (Pyricularia oryzae) or irradiated with UV light.[3] More recently it has been shown to be a potential chemotherapeutic agent against human colon cancer.[4]
Biosynthesis
[edit]Of the 15 phytoalexins that have been isolated from rice, 14, including momilactone B, are diterpenes commonly biosynthesized from geranylgeranyl diphosphate (GGDP). Research on the synthetic pathway for momilactone B has found it involves a set of enzymes that are encoded by genes located on chromosome 4.[citation needed]
The first step in the biosynthesis of momilactone B is the cyclization of GGDP to syn-copalyl diphosphate (syn-CDP), a type B[clarification needed] cyclization. This is initiated by the addition of a proton to the terminal olefin bond of GGDP. The genes encoding for syn-CDP synthase was found by Otomo et al.. in 2004.[5] This was labeled as OsCyc1 (Oryza sativa Cyclase 1). According to the rice genome database, OsCyc1 corresponds to OsCPS4 (AL662933) found in chromosome 4 (14.3cM) discovered by Sakamoto et al.. in 2004.[6]
The second step is the cyclization of syn-CDP to 9β-pimara-7,15-diene. This step is initiated by the elimination of the diphosphate group, a type A[clarification needed] cyclization. The genes encoding for the type A cyclase were found by Otomo et al.. in 2004.[7] It is suggested that OsKS4, located on chromosome 4 (14.3cM) is one of the genes responsible for phytoalexin biosynthesis. After UV-radiation, OsKS4 mRNA levels rise drastically in response to the attack.
Further oxidation of the 9β-pimara-7,15-diene compound followed by lactone and lactol formation yields momilactone B. Though the gene sequence of these oxidations is unknown, P450 monooxygenase genes have been identified near the cyclase genes on chromosome 4.
Stereochemistry
[edit]The stereochemistry reported by Kato et al. in 1973[1] is different than that shown in the biosynthesis references. The stereochemistry of momilactone B shown here is based on the biosynthesis references.[5][6][7] There are no known papers correcting the stereochemistry from the isolation paper.
References
[edit]- ^ a b Kato, T.; Kabuto, C.; Sasaki, N.; Tsunagawa, M.; Aizawa, H.; Fujita, K.; Kato, Y.; Kitahara, Y. (1973). "Momilactones, Growth Inhibitors from Rice, Oryza Sativa L.". Tetrahedron Lett. 14 (39): 3861–3864. doi:10.1016/S0040-4039(01)87058-1.
- ^ Toyomasu, T.; Kagahara, T.; Okada, K.; Koga, J.; Hasegawa, M.; Mitsuhashi, W.; Sassa, T.; Yamane, H. (2008). "Diterpene Phytoalexins are Biosynthesized in and Exuded from the Roots of Rice Seedlings". Biosci. Biotechnol. Biochem. 72 (2): 562–567. doi:10.1271/bbb.70677. PMID 18256463.
- ^ Cartwright, D. W.; Langcake, P.; Pryce, R. J.; Leworthy, D. P.; Ride, J. P. (1981). "Isolation and Characterization of Two Phytoalexins from Rice as Momilactones A and B". Phytochemistry. 20 (3): 535–537. Bibcode:1981PChem..20..535C. doi:10.1016/S0031-9422(00)84189-8.
- ^ Kim, S.; Park, H.; Park, E.; Lee, S. (2007). "Cytotoxic and Antitumor Activity of Momilactone B from Rice Hulls". J. Agric. Food Chem. 55 (5): 1702–1706. doi:10.1021/jf062020b. PMID 17326606.
- ^ a b Otomo, K.; Kenmoku, H.; Oikawa, H.; König, W. A.; Toshima, H.; Mitsuhashi, W.; Yamane, H.; Sassa, T.; Toyomasu, T. (2004). "Biological functions of ent- and syn-copalyl diphosphate synthases in rice: key enzymes for the branch point of gibberellin and phytoalexin biosynthesis". Plant J. 39 (6): 886–893. doi:10.1111/j.1365-313X.2004.02175.x. PMID 15341631.
- ^ a b Sakamoto, T.; Miura, K.; Itoh, H.; Tatsumi, T.; Ueguchi-Tanaka, M.; Ishiyama, K.; Kobayashi, M.; Agrawal, G. K.; Takeda, S.; Abe, K.; Miyao, A.; Hirochika, H.; Kitano, H.; Ashikari, M.; Matsuoka, M. (2004). "An Overview of Gibberellin Metabolism Enzyme Genes and Their Related Mutants in Rice". Plant Physiol. 134 (4): 1642–1653. doi:10.1104/pp.103.033696. PMC 419838. PMID 15075394.
- ^ a b Otomo, K.; Kanno, Y.; Motegi, A.; Kenmoku, H.; Yamane, H.; Mitsuhashi, W.; Oikawa, H.; Toshima, H.; Itoh, H.; Matsuoka, M.; Sassa, T.; Toyomasu, T. (2004). "Diterpene Cyclases Responsible for the Biosynthesis of Phytoalexins, Momilactones A, B, and Oryzalexins A-F in Rice". Biosci. Biotechnol. Biochem. 68 (9): 2001–2006. doi:10.1271/bbb.68.2001. PMID 15388982. S2CID 9892116.