Amavadin: Difference between revisions

Amavadin
Names
	IUPAC name bis[N-[(1S)-1-(carboxy-κO)ethyl]-N-(hydroxy-κO)-L-alaninato(2-)-.κN,κO]-vanadium
Identifiers
CAS Number	12705-99-6 ;
3D model (JSmol)	Interactive image;
ChemSpider	52085372 dihydric acid;
PubChem CID	119025631 dihydric acid;
UNII	5J3H8J7S42;
	InChI InChI=1S/2C6H10NO5.V/c21-3(5(8)9)7(12)4(2)6(10)11;/h23-4H,1-2H3,(H,8,9)(H,10,11);/q2*-1;+4/p-4 Key: JFEAKSQUSDDXGF-UHFFFAOYSA-J;
	SMILES CC(C(=O)[O-])N(C(C)C(=O)[O-])[O-].CC(C(=O)[O-])N(C(C)C(=O)[O-])[O-].[V+4];
Properties
Chemical formula	[V{NO[CH(CH3)CO2]2}2]2−
Molar mass	398.94 g/mol
Appearance	Light blue in solution
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

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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.^[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 precursor found in amavadin (left), the ligand (center) and H₃(HIDA) (right).

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 twofold 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.

Biological function

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. (1999). "The Structural Characterization of Amavadin". Angew. Chem. Int. Ed. 38 (6): 795–797. doi:10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7. PMID 29711812.
^ 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. Kneifel, H.; Bayer, E. (1986). "Stereochemistry and total synthesis of amavadin, the naturally occurring vanadium compound of Amanita muscaria". Journal of the American Chemical Society. 108 (11): 3075–3077. doi:10.1021/ja00271a043..
^ ^a ^b ^c Hubregtse, T.; Neeleman, E.; Maschmeyer, T.; Sheldon, R.A.; Hanefeld, U.; Arends, I.W.C.E. (2005). "The first enantioselective synthesis of the amavadin ligand and its complexation to vanadium". J. Inorg. Biochem. 99 (5): 1264–1267. doi:10.1016/j.jinorgbio.2005.02.004. PMID 15833352.
^ Fu, S-C.J.; Birnbaum, S.M.; Greenstein, J.P. (1954). "Influence of Optically Active Acyl Groups on the Enzymatic Hydrolysis of N-Acylated-L-amino Acids". J. Am. Chem. Soc. 76 (23): 6054–6058. doi:10.1021/ja01652a057.
^ Armstrong, E.M.; Beddoes, R.L.; Calviou, L.J.; Charnock, J.M.; Collison, D.; Ertok, N.; Naismith, J.H.; Garner, C.D. (1993). "The Chemical Nature of Amavadin". J. Am. Chem. Soc. 115 (2): 807–808. doi:10.1021/ja00055a073.
^ Garner, C.D.; Armstrong, E.M.; Berry, R.E.; Beddoes, R.L.; Collison, D.; Cooney, J.J.A.; Ertok, S.N.; Helliwell, M. (2000). "Investigations of Amavadin". J. Inorg. Biochem. 80 (1–2): 17–20. doi:10.1016/S0162-0134(00)00034-9. PMID 10885458.

[Berry-1] Berry, R.E.; Armstrong, E.M.; Beddoes, R.L.; Collison, D.; Ertok, S.N.; Helliwell, M.; Garner, C.D. (1999). "The Structural Characterization of Amavadin". Angew. Chem. Int. Ed. 38 (6): 795–797. doi:10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7. PMID 29711812.

[2] 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. Kneifel, H.; Bayer, E. (1986). "Stereochemistry and total synthesis of amavadin, the naturally occurring vanadium compound of Amanita muscaria". Journal of the American Chemical Society. 108 (11): 3075–3077. doi:10.1021/ja00271a043..

[Hub-3] Hubregtse, T.; Neeleman, E.; Maschmeyer, T.; Sheldon, R.A.; Hanefeld, U.; Arends, I.W.C.E. (2005). "The first enantioselective synthesis of the amavadin ligand and its complexation to vanadium". J. Inorg. Biochem. 99 (5): 1264–1267. doi:10.1016/j.jinorgbio.2005.02.004. PMID 15833352.

[4] Fu, S-C.J.; Birnbaum, S.M.; Greenstein, J.P. (1954). "Influence of Optically Active Acyl Groups on the Enzymatic Hydrolysis of N-Acylated-L-amino Acids". J. Am. Chem. Soc. 76 (23): 6054–6058. doi:10.1021/ja01652a057.

[5] Armstrong, E.M.; Beddoes, R.L.; Calviou, L.J.; Charnock, J.M.; Collison, D.; Ertok, N.; Naismith, J.H.; Garner, C.D. (1993). "The Chemical Nature of Amavadin". J. Am. Chem. Soc. 115 (2): 807–808. doi:10.1021/ja00055a073.

[6] Garner, C.D.; Armstrong, E.M.; Berry, R.E.; Beddoes, R.L.; Collison, D.; Cooney, J.J.A.; Ertok, S.N.; Helliwell, M. (2000). "Investigations of Amavadin". J. Inorg. Biochem. 80 (1–2): 17–20. doi:10.1016/S0162-0134(00)00034-9. PMID 10885458.

[1]

[2]

[3]

[4]

[5]

[6]

@@ Line 10: / Line 10: @@
 | CASNo_Ref = {{cascite|correct|??}}
 | CASNo = 12705-99-6
-| PubChem =
+| PubChem = 119025631
+| PubChem_Comment = dihydric acid
-| SMILES = }}
+| ChemSpiderID = 52085372
+| ChemSpiderID_Comment = dihydric acid
+| UNII = 5J3H8J7S42
+| SMILES = CC(C(=O)[O-])N(C(C)C(=O)[O-])[O-].CC(C(=O)[O-])N(C(C)C(=O)[O-])[O-].[V+4]
+| StdInChI=1S/2C6H10NO5.V/c2*1-3(5(8)9)7(12)4(2)6(10)11;/h2*3-4H,1-2H3,(H,8,9)(H,10,11);/q2*-1;+4/p-4
+| StdInChIKey = JFEAKSQUSDDXGF-UHFFFAOYSA-J
+}}
 |Section2={{Chembox Properties
 | Formula = [V{NO[CH(CH<sub>3</sub>)CO<sub>2</sub>]<sub>2</sub>}<sub>2</sub>]<sup>2−</sup>
@@ Line 26: / Line 34: @@
 }}
+'''Amavadin''' is a [[vanadium]]-containing [[anion]] found in three species of poisonous ''[[Amanita]]'' mushrooms: ''[[Amanita muscaria|A. muscaria]]'', ''A. regalis'', and ''A. velatipes''.<ref name=Berry>{{cite journal |author1=Berry, R.E. |author2=Armstrong, E.M. |author3=Beddoes, R.L. |author4=Collison, D. |author5=Ertok, S.N. |author6=Helliwell, M. |author7=Garner, C.D. | title = The Structural Characterization of Amavadin | journal = Angew. Chem. Int. Ed. | year = 1999 | volume = 38 | issue = 6 | pages =  795&ndash;797 | doi = 10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7 | pmid=29711812| doi-access=free }}</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&ndash;3077. {{Cite journal| first1 = H.| first2 = E.| title = Stereochemistry and total synthesis of amavadin, the naturally occurring vanadium compound of Amanita muscaria| last1 = Kneifel| journal = Journal of the American Chemical Society| volume = 108| issue =  11| pages = 3075–3077| year = 1986| doi = 10.1021/ja00271a043| last2 =  Bayer}}.</ref> This anion, which appears as a blue solution, is an eight-coordinate vanadium [[complex (chemistry)|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>{{cite journal |author1=Hubregtse, T. |author2=Neeleman, E. |author3=Maschmeyer, T. |author4=Sheldon, R.A. |author5=Hanefeld, U. |author6=Arends, I.W.C.E. | title = The first enantioselective synthesis of the amavadin ligand and its complexation to vanadium | journal = J. Inorg. Biochem. | year = 2005 | volume = 99 | pages = 1264&ndash;1267 | doi = 10.1016/j.jinorgbio.2005.02.004 | pmid=15833352 | issue = 5}}</ref>
-[[File:Amanita muscaria 3 vliegenzwammen op rij.jpg|thumb| right| ''Amanita muscaria'' contains amavadin]]
+[[File:Amanita muscaria 3 vliegenzwammen op rij.jpg|thumb|left| ''Amanita muscaria'' contains amavadin]]
-'''Amavadin''' is a [[vanadium]]-containing [[anion]] found in three species of poisonous ''[[Amanita]]'' mushrooms: ''[[Amanita muscaria|A. muscaria]]'', ''A. regalis'', and ''A. velatipes''.<ref name=Berry>{{cite journal |author1=Berry, R.E. |author2=Armstrong, E.M. |author3=Beddoes, R.L. |author4=Collison, D. |author5=Ertok, S.N. |author6=Helliwell, M. |author7=Garner, C.D. | title = The Structural Characterization of Amavadin | journal = Angew. Chem. Int. Ed. | year = 1999 | volume = 38 | issue = 6 | pages =  795&ndash;797 | 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&ndash;3077. {{Cite journal| first1 = H.| first2 = E.| title = Stereochemistry and total synthesis of amavadin, the naturally occurring vanadium compound of Amanita muscaria| last1 = Kneifel| journal = Journal of the American Chemical Society| volume = 108| issue =  11| pages = 3075–3077| year = 1986| doi = 10.1021/ja00271a043| last2 =  Bayer}}.</ref> This anion, which appears as a blue solution, is an eight-coordinate vanadium [[complex (chemistry)|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>{{cite journal |author1=Hubregtse, T. |author2=Neeleman, E. |author3=Maschmeyer, T. |author4=Sheldon, R.A. |author5=Hanefeld, U. |author6=Arends, I.W.C.E. | title = The first enantioselective synthesis of the amavadin ligand and its complexation to vanadium | journal = J. Of Inorg. Biochem. | year = 2005 | volume = 99 | pages = 1264&ndash;1267 | doi = 10.1016/j.jinorgbio.2005.02.004 | pmid=15833352 | issue = 5}}</ref>
 ==Preparation==
 The formation of amavadin begins with the formation of two tetradentate [[ligand]]s.<ref name=Hub/>
 :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>
 ==Structure and properties==
+[[File:AmavadinRevd.png|380px|thumb|left|The ligand precursor found in amavadin (left), the ligand (center) and H<sub>3</sub>(HIDA) (right).]]
 The ligand found in amavadin was first synthesized in 1954.<ref>{{cite journal |author1=Fu, S-C.J. |author2=Birnbaum, S.M. |author3=Greenstein, J.P. | title = Influence of Optically Active Acyl Groups on the Enzymatic Hydrolysis of N-Acylated-L-amino Acids | journal = J. Am. Chem. Soc. | year = 1954 | volume = 76 | issue = 23 | pages = 6054&ndash;6058 | 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>{{cite journal |author1=Armstrong, E.M. |author2=Beddoes, R.L. |author3=Calviou, L.J. |author4=Charnock, J.M. |author5=Collison, D. |author6=Ertok, N. |author7=Naismith, J.H. |author8=Garner, C.D. | title = The Chemical Nature of Amavadin | journal = J. Am. Chem. Soc. | year = 1993 | volume = 115 | issue = 2 | pages = 807&ndash;808 | doi = 10.1021/ja00055a073}}</ref> The ligands coordinate through the nitrogen and the three oxygen centers.
 Amavadin is a C<sub>2</sub>-symmetric anion with a 2− charge. The twofold 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.
-[[Image:AmavadinRevd.png|380px|thumb|left|The ligand precursor found in amavadin (left), the ligand (center), and H<sub>3</sub> (HIDA, right).]]{{clear-left}}
 == Biological function ==
-The biological function of amavadin is still unknown, yet it has been thought that it uses H<sub>2</sub>O<sub>2</sub> and acts as a [[peroxidase]] to aid the regeneration of damaged tissues.<ref name="Hub" /> Amavadin may serve as a toxin for protection of the mushroom.<ref>{{cite journal |author1=Garner, C.D. |author2=Armstrong, E.M. |author3=Berry, R.E. |author4=Beddoes, R.L. |author5=Collison, D. |author6=Cooney, J.J.A. |author7=Ertok, S.N. |author8=Helliwell, M. | title = Investigations of Amavadin | journal = J. Of Inorg. Biochem. | year = 2000 | volume = 80 | pages = 17&ndash;20 | doi=10.1016/S0162-0134(00)00034-9 | pmid=10885458 | issue = 1–2}}</ref>
+The biological function of amavadin is still unknown, yet it has been thought that it uses H<sub>2</sub>O<sub>2</sub> and acts as a [[peroxidase]] to aid the regeneration of damaged tissues.<ref name="Hub" /> Amavadin may serve as a toxin for protection of the mushroom.<ref>{{cite journal |author1=Garner, C.D. |author2=Armstrong, E.M. |author3=Berry, R.E. |author4=Beddoes, R.L. |author5=Collison, D. |author6=Cooney, J.J.A. |author7=Ertok, S.N. |author8=Helliwell, M. | title = Investigations of Amavadin | journal = J. Inorg. Biochem. | year = 2000 | volume = 80 | pages = 17&ndash;20 | doi=10.1016/S0162-0134(00)00034-9 | pmid=10885458 | issue = 1–2}}</ref>
+{{clear-left}}
 == References ==
@@ Line 49: / Line 58: @@
 {{Poisonous Amanitas}}
-[[Category:Vanadium compounds]]
+[[Category:Vanadium(V) compounds]]
 [[Category:Mycotoxins found in Basidiomycota]]