4-Amino-5-hexenoic acid

Nucleophilic groups from enzymes can add to double bonds, e.g., in an aminoacrylate Schiff base, or to multiple bonds present in die inhibitor. An example is y-vinyl y-aminobutyrate (4-amino-5-hexenoic acid), another inhibitor of brain y-aminobutyrate aminotransferase which is a useful anticonvulsant drug. 

A suspension of ethyl 4-trichloroacetoamido-5-hexanoate (0.3 g, 1 mmol) in 6 N HCI (10 mL) was heated under reflux 6 hours. Then the mixture was concentrated in vacuo, diluted with water (10 mL), washed twice with AcOEt, and dried in uacuo to give the title product (0.18 g, 100%). NMR, TLC (NH4OH EtOH, 3 7) are identical with those of an authentic sample of 4-amino-5-hexenoic acid. 

Hatanaka S, Furukawa J, Aoki T, Akatsuka H, Nagasawa E (1994) (2S)-2-Amino-5-chloro-4-hydroxy-5-hexenoic Acid, a New Chloroamino Acid, and Related Compounds from Amanita gymnopus. My coscience 35 391... 

High cis selectivity has been observed in the halolactonization of 2-amino-5-substituted (Z)- and ( )-4-pentenoie acids. Treatment of (S)-(Z)-2-/m-butoxycarbonylamino-6-hydroxy-4-hexenoic acid [(S)-(Z)-8] with A -bromosuccinitrude in tetrahydrofuran at 0 °C for 5 minutes gives a 90 10 mixture of the cisjtrans-y-lactone 9 in 95% yield41. The major n.s-isomer can be purified by crystallization from chloroform/hexane. 

More highly functionalized products can be obtained, often in better yield, by the ene reaction of a-substituted acrylate esters. EtAlCb is a more effective catalyst than AlCb for these reactions because it is a Brpnsted base as well as a Lewis acid. The EtAlCb catdyzed reactions of methyl a-bromo- and a-chloro-acrylate with trans-1,2-disubstituted and trisubstituted alkenes are both regio- and stereo-specific. - The major product (13a 85-95%) is formed via transition state (12a) in which the methoxycar-bonyl group is endo. The stereochemistry of the major adduct was established by the stereospecific conversion of (13a) to both diastereomers of ( )-2-amino-4-methyl-5-hexenoic acid and confirmed by X-ray crystallographic analysis in a related system. ... 

Ojea, V., Conde, S., Ruiz, M., Fernandez, M.C., and Quintela, J.M., Conjugate addition of lithiated Schdllkopf s bislactim ether to l , 3 -butadienylphosphonates. Stereocontrolled access to 2,3-anti-4 -2-amino-6-phosphono-4-hexenoic acid derivatives. Tetrahedron Lett., 38, 4311, 1997. 

Ilamycins (Rufomycin) S. islandicus Acid-fast bacteria 1,100 Ala, Leu, Me-Leu, y-formyl-mcthyl-norvaline, 3-nitro-4-hydroxy-Phe, Try, 2-amino-4-hexenoic acid... 

Vigabatrin, 4-Amino-S-hexenoic acid >-vinyl aminobutyric acid gamma-vinyl GABA GABA ... 

Figure 3.58 Proposed pathway for the biosynthesis of 2-amino-3,5-dimethyl-4-hexenoic acid (ADH) from valine and pyruvate in S. arenicola. 1° denotes primary enzymatic reactions in S. arenicola encoded by genes outside the cym cluster.

Amino-2-hexenoic acid, A-60167 2-Amino-3-hexenoic acid, A-60168... 

---