Amavadin: Difference between revisions
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'''Amavadin''' is a [[vanadium]]-containing [[anion]] found in three species of poisonous Amanita mushrooms: ''A. muscaria'', ''A. regalis'', and ''A. velatipes''.<ref name=Berry>Berry, R.E.; Armstrong, E.M.; Beddoes, R.L.; Collison, D.; Ertok, S.N.; Helliwell, M.; Garner, C.D. “The Structural Characterization of Amavadin.” Angew. Chem. Int. Ed. 1999, 38:6, pp. 795-797. {{Cite doi| 10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7}}.</ref> Amavadin was first isolated and identified in 1972 by Kneifel and Bayer.<ref>Kneifel, H.; Bayer, E. “Stereochemistry and total synthesis of amavadin, the naturally occurring vanadium anion of Amanita muscaria.” J. Am. Chem. Soc. 1986, 108:11, pp. 3075-3077. {{Cite doi|10.1021/ja00271a043}}.</ref> This anion, which appears as a blue solution, is an eight-coordinate vanadium complex.<ref name="Berry" /> A Ca<sup>2+</sup> cation is often used to crystallize amavadin to obtain a good quality X-ray diffraction.<ref name=Berry/> Oxidized amavadin can be isolated as its PPh<sub>4</sub><sup>+</sup> salt. The oxidized form contains vanadium (V), which can be used to obtain an NMR spectrum.<ref name=Hub>Hubregtse, T.; Neeleman, E.; Maschmeyer, T.; Sheldon, R.A.;, Hanefeld, U.; Arends, I.W.C.E. “The first enantioselective synthesis of the amavadin ligand and its complexation to vanadium.” J. of Inorg. Biochem. 2005, 99, pp. 1264-1267. {{Cite doi|10.1016/j.jinorgbio.2005.02.004}}.</ref> |
'''Amavadin''' is a [[vanadium]]-containing [[anion]] found in three species of poisonous Amanita mushrooms: ''A. muscaria'', ''A. regalis'', and ''A. velatipes''.<ref name=Berry>Berry, R.E.; Armstrong, E.M.; Beddoes, R.L.; Collison, D.; Ertok, S.N.; Helliwell, M.; Garner, C.D. “The Structural Characterization of Amavadin.” Angew. Chem. Int. Ed. 1999, 38:6, pp. 795-797. {{Cite doi| 10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7}}.</ref> Amavadin was first isolated and identified in 1972 by Kneifel and Bayer.<ref>Kneifel, H.; Bayer, E. “Stereochemistry and total synthesis of amavadin, the naturally occurring vanadium anion of Amanita muscaria.” J. Am. Chem. Soc. 1986, 108:11, pp. 3075-3077. {{Cite doi|10.1021/ja00271a043}}.</ref> This anion, which appears as a blue solution, is an eight-coordinate vanadium complex.<ref name="Berry" /> A Ca<sup>2+</sup> cation is often used to crystallize amavadin to obtain a good quality X-ray diffraction.<ref name=Berry/> Oxidized amavadin can be isolated as its PPh<sub>4</sub><sup>+</sup> salt. The oxidized form contains vanadium (V), which can be used to obtain an NMR spectrum.<ref name=Hub>Hubregtse, T.; Neeleman, E.; Maschmeyer, T.; Sheldon, R.A.;, Hanefeld, U.; Arends, I.W.C.E. “The first enantioselective synthesis of the amavadin ligand and its complexation to vanadium.” J. of Inorg. Biochem. 2005, 99, pp. 1264-1267. {{Cite doi|10.1016/j.jinorgbio.2005.02.004}}.</ref> |
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The formation of amavadin begins with the formation of two tetradentate [[ligand]]s.<ref name=Hub/> |
The formation of amavadin begins with the formation of two tetradentate [[ligand]]s.<ref name=Hub/> |
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:2 HON(CH(CH<sub>3</sub>)CO<sub>2</sub>H)<sub>2</sub> + VO<sup>2+</sup> → [V{NO[CH(CH<sub>3</sub>)CO<sub>2</sub>]<sub>2</sub>}<sub>2</sub>]<sup>2-</sup> + H<sub>2</sub>O + |
:2 HON(CH(CH<sub>3</sub>)CO<sub>2</sub>H)<sub>2</sub> + VO<sup>2+</sup> → [V{NO[CH(CH<sub>3</sub>)CO<sub>2</sub>]<sub>2</sub>}<sub>2</sub>]<sup>2-</sup> + H<sub>2</sub>O + 4 H<sup>+</sup> |
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==Structure and properties== |
==Structure and properties== |
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The ligand found in amavadin was first synthesized in 1954.<ref>Fu, S-C.J.; Birnbaum, S.M.; Greenstein, J.P. “Influence of Optically Active Acyl Groups on the Enzymatic Hydrolysis of N-Acylated-L-amino Acids.” J. Am. Chem. Soc. 1954, 76:23, pp. 6054-6058. {{Cite doi| 10.1021/ja01652a057}}.</ref> Amavadin contains vanadium (IV). Initially, amavadin was thought to have a vanadyl, VO<sup>2+</sup>, center. In 1993, it was discovered by crystallographic characterization that amavadin is not a [[vanadyl ion]] compound. Instead, it is an octacoordinated vanadium (IV) complex. This complex is bonded to two tetradentate ligands derived from N-hydroxyimino-2,2'-dipropionic acid, H<sub>3</sub>(HIDPA), ligands.<ref>Armstrong, E.M.; Beddoes, R.L.; Calviou, L.J.; Charnock, J.M.; Collison, D.; Ertok, N.; Naismith, J.H.; Garner, C.D. “The Chemical Nature of Amavadin. J. Am. Chem. Soc. 1993, 115:2, pp. 807-808. {{Cite doi| 10.1021/ja00055a073}}.</ref> The ligands coordinate through the nitrogen and the three oxygen centers. |
The ligand found in amavadin was first synthesized in 1954.<ref>Fu, S-C.J.; Birnbaum, S.M.; Greenstein, J.P. “Influence of Optically Active Acyl Groups on the Enzymatic Hydrolysis of N-Acylated-L-amino Acids.” J. Am. Chem. Soc. 1954, 76:23, pp. 6054-6058. {{Cite doi| 10.1021/ja01652a057}}.</ref> Amavadin contains vanadium (IV). Initially, amavadin was thought to have a vanadyl, VO<sup>2+</sup>, center. In 1993, it was discovered by crystallographic characterization that amavadin is not a [[vanadyl ion]] compound. Instead, it is an octacoordinated vanadium (IV) complex. This complex is bonded to two tetradentate ligands derived from N-hydroxyimino-2,2'-dipropionic acid, H<sub>3</sub>(HIDPA), ligands.<ref>Armstrong, E.M.; Beddoes, R.L.; Calviou, L.J.; Charnock, J.M.; Collison, D.; Ertok, N.; Naismith, J.H.; Garner, C.D. “The Chemical Nature of Amavadin. J. Am. Chem. Soc. 1993, 115:2, pp. 807-808. {{Cite doi| 10.1021/ja00055a073}}.</ref> The ligands coordinate through the nitrogen and the three oxygen centers. |
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Amavadin is a C<sub>2</sub>-symmetric anion with a 2- charge. The two-fold axis bisects the vanadium atom perpendicular to the two NO ligands. The anion features five chiral centers, one at vanadium and the four carbon atoms having S stereochemistry.<ref name="Berry" /> There are two possible diastereomers for the ligands, (S,S)-(S,S)-Δ and (S,S)-(S,S)-Λ. |
Amavadin is a C<sub>2</sub>-symmetric anion with a 2- charge. The two-fold axis bisects the vanadium atom perpendicular to the two NO ligands. The anion features five chiral centers, one at vanadium and the four carbon atoms having S stereochemistry.<ref name="Berry" /> There are two possible diastereomers for the ligands, (S,S)-(S,S)-Δ and (S,S)-(S,S)-Λ. |
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Revision as of 04:13, 29 April 2009
Amavadin is a vanadium-containing anion found in three species of poisonous Amanita mushrooms: A. muscaria, A. regalis, and A. velatipes.[1] Amavadin was first isolated and identified in 1972 by Kneifel and Bayer.[2] This anion, which appears as a blue solution, is an eight-coordinate vanadium complex.[1] A Ca2+ cation is often used to crystallize amavadin to obtain a good quality X-ray diffraction.[1] Oxidized amavadin can be isolated as its PPh4+ salt. The oxidized form contains vanadium (V), which can be used to obtain an NMR spectrum.[3]
Preparation
The formation of amavadin begins with the formation of two tetradentate ligands.[3]
- 2 HON(CH(CH3)CO2H)2 + VO2+ → [V{NO[CH(CH3)CO2]2}2]2- + H2O + 4 H+
Structure and properties
The ligand found in amavadin was first synthesized in 1954.[4] Amavadin contains vanadium (IV). Initially, amavadin was thought to have a vanadyl, VO2+, center. In 1993, it was discovered by crystallographic characterization that amavadin is not a vanadyl ion compound. Instead, it is an octacoordinated vanadium (IV) complex. This complex is bonded to two tetradentate ligands derived from N-hydroxyimino-2,2'-dipropionic acid, H3(HIDPA), ligands.[5] The ligands coordinate through the nitrogen and the three oxygen centers.
Amavadin is a C2-symmetric anion with a 2- charge. The two-fold axis bisects the vanadium atom perpendicular to the two NO ligands. The anion features five chiral centers, one at vanadium and the four carbon atoms having S stereochemistry.[1] There are two possible diastereomers for the ligands, (S,S)-(S,S)-Δ and (S,S)-(S,S)-Λ.
The biological function of amavadin is still unknown, yet it has been thought that it uses H2O2 and acts as a peroxidase to aid the regeneration of damaged tissues.[3] Amavadin may serve as a toxin for protection of the mushroom.[6]
References
- ^ a b c d Berry, R.E.; Armstrong, E.M.; Beddoes, R.L.; Collison, D.; Ertok, S.N.; Helliwell, M.; Garner, C.D. “The Structural Characterization of Amavadin.” Angew. Chem. Int. Ed. 1999, 38:6, pp. 795-797. Attention: This template ({{cite doi}}) is deprecated. To cite the publication identified by doi: 10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7, please use {{cite journal}} (if it was published in a bona fide academic journal, otherwise {{cite report}} with
|doi= 10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7instead.. - ^ Kneifel, H.; Bayer, E. “Stereochemistry and total synthesis of amavadin, the naturally occurring vanadium anion of Amanita muscaria.” J. Am. Chem. Soc. 1986, 108:11, pp. 3075-3077. Attention: This template ({{cite doi}}) is deprecated. To cite the publication identified by doi:10.1021/ja00271a043, please use {{cite journal}} (if it was published in a bona fide academic journal, otherwise {{cite report}} with
|doi=10.1021/ja00271a043instead.. - ^ a b c Hubregtse, T.; Neeleman, E.; Maschmeyer, T.; Sheldon, R.A.;, Hanefeld, U.; Arends, I.W.C.E. “The first enantioselective synthesis of the amavadin ligand and its complexation to vanadium.” J. of Inorg. Biochem. 2005, 99, pp. 1264-1267. Attention: This template ({{cite doi}}) is deprecated. To cite the publication identified by doi:10.1016/j.jinorgbio.2005.02.004, please use {{cite journal}} (if it was published in a bona fide academic journal, otherwise {{cite report}} with
|doi=10.1016/j.jinorgbio.2005.02.004instead.. - ^ Fu, S-C.J.; Birnbaum, S.M.; Greenstein, J.P. “Influence of Optically Active Acyl Groups on the Enzymatic Hydrolysis of N-Acylated-L-amino Acids.” J. Am. Chem. Soc. 1954, 76:23, pp. 6054-6058. Attention: This template ({{cite doi}}) is deprecated. To cite the publication identified by doi: 10.1021/ja01652a057, please use {{cite journal}} (if it was published in a bona fide academic journal, otherwise {{cite report}} with
|doi= 10.1021/ja01652a057instead.. - ^ Armstrong, E.M.; Beddoes, R.L.; Calviou, L.J.; Charnock, J.M.; Collison, D.; Ertok, N.; Naismith, J.H.; Garner, C.D. “The Chemical Nature of Amavadin. J. Am. Chem. Soc. 1993, 115:2, pp. 807-808. Attention: This template ({{cite doi}}) is deprecated. To cite the publication identified by doi: 10.1021/ja00055a073, please use {{cite journal}} (if it was published in a bona fide academic journal, otherwise {{cite report}} with
|doi= 10.1021/ja00055a073instead.. - ^ Garner, C.D.; Armstrong, E.M.; Berry, R.E.; Beddoes, R.L.; Collison, D.; Cooney, J.J.A.; Ertok, S.N.; Helliwell, M. “Investigations of Amavadin.” J. of Inorg. Biochem. 2000, 80, pp. 17-20. Attention: This template ({{cite doi}}) is deprecated. To cite the publication identified by doi:10.1016/S0162-0134(00)00034-9, please use {{cite journal}} (if it was published in a bona fide academic journal, otherwise {{cite report}} with
|doi=10.1016/S0162-0134(00)00034-9instead..