Vanadyl acetylacetonate explained

Vanadyl acetylacetonate is the chemical compound with the formula VO(acac)2, where acac is the conjugate base of acetylacetone. It is a blue-green solid that dissolves in polar organic solvents. The coordination complex consists of the vanadyl group, VO2+, bound to two acac ligands via the two oxygen atoms on each. Like other charge-neutral acetylacetonate complexes, it is not soluble in water.

Synthesis

The complex is generally prepared from vanadium(IV), e.g. vanadyl sulfate:[1]

VOSO4 + 2 Hacac → VO(acac)2 + H2SO4

It can also be prepared by a redox reaction starting with vanadium pentoxide. In this reaction, some acetylacetone is oxidized to 2,3,4-Pentanetrione.[1]

Structure and properties

The complex has a square pyramidal structure with a short V=O bond. This d1 compound is paramagnetic. Its optical spectrum exhibits two transitions. It is a weak Lewis acid, forming adducts with pyridine and methylamine.[1]

Applications

It is used in organic chemistry as a catalyst for the epoxidation of allylic alcohols by tert-butyl hydroperoxide (TBHP). The VO(acac)2–TBHP system exclusively epoxidizes geraniol at the allylic alcohol position, leaving the other alkene of geraniol untouched. By comparison, m-CPBA, another epoxidizing agent, reacts with both alkenes, creating the products in a two to one ratio favoring reaction at the alkene away from the hydroxyl group. TBHP oxidizes VO(acac)2 to a vanadium(V) species which coordinates the alcohol of the substrate and the hydroperoxide, directing the epoxidation to occur at the alkene close to this coordination site.[2] [3]

Biomedical aspects

Vanadyl acetylacetonate exhibits insulin mimetic properties, in that it can stimulate the phosphorylation of protein kinase B (PKB/Akt) and glycogen synthase kinase 3 (GSK-3).[4] It has also been shown inhibit tyrosine phosphatase (PTPase), PTPases such as PTP1B, which dephosphorylates insulin receptor beta subunit, thus increasing its phosphorylation, allowing for a prolonged activation of IRS-1, PKB, and GSK-3, allowing them to exert their anti-diabetic properties.

External links

References

  1. Book: Richard A. . Rowe . Mark M. . Jones . Vanadium(IV) Oxy(acetylacetonate) . Inorganic Syntheses . . 1957 . 5 . 113–116 . 10.1002/9780470132364.ch30 . 978-0-470-13236-4.
  2. Takashi . Itoh . Koichiro . Jitsukawa . Kiyotomi . Kaneda . Shiichiro . Teranishi . Vanadium-catalyzed epoxidation of cyclic allylic alcohols. Stereoselectivity and stereocontrol mechanism . . 1979 . 101 . 1 . 159–169 . 10.1021/ja00495a027.
  3. Encyclopedia: Bryant E. . Rossiter . Hsyueh-Liang . Wu . Toshikazu . Hirao . Vanadyl Bis(acetylacetonate) . Encyclopedia of Reagents for Organic Synthesis . John Wiley & Sons . 2007-03-15 . 10.1002/047084289X.rv003m.pub2. 978-0-471-93623-7 .
  4. Mohamad Z. . Mehdi . Ashok K. . Srivastava . Organo-vanadium compounds are potent activators of the protein kinase B signaling pathway and protein tyrosine phosphorylation: Mechanism of insulinomimesis . . 2005 . 440 . 158–164 . 10.1016/j.abb.2005.06.008 . 16055077 . 2.