Biosynthesis of Acyl Moieties of Capsaicin and its Analogues from Valine and Leucine in Capsicum Fruits

Biosynthetic pathways of acyl moieties of capsaicinoid in intactCapsicum fruits and spheroplasts prepared from placentas ofCapsicum fruits were examined using a radioisotopic technique.In intact Capsicum fruits, L-U-¹⁴C] valine was incorporatedinto capsaicin and dihydrocapsaicin, the acyl constituents ofwhich are even-number branched chain fatty acids, while L-U-¹⁴C]leucine was incorporated into nordihydrocapsaicin and homodihydrocapsaicin,which have odd-number branched chain facty acids as the acylmoieties. The intermediates of the odd- and even-number branchedchain fatty acids were identified with GLC/GPC after the spheroplastshad been incubated with L-U-¹⁴C] valine or L-U-¹⁴C] leucine.After incubation with L-U-¹⁴C] valine, isobutyric acid and8-methyl nonanoic acid were detected, while isopentanoic acidand 9-methyl decanoic acid were found after incubation withL-U-¹⁴C] leucine. The involvement of a-ketoisovalerate or a-ketoisocaproatein the biosynthesis of acyl moieties of capsaicinoid was alsodemonstrated in vitro using cell-free extracts of the placentasof Capsicum fruits. These findings suggest that the acyl moietiesof individual capsaicinoids in Capsicum fruits are synthesizedby pathways similar to those proposed for adipose tissue andbacteria. ¹Formation and Metabolism of Pungent Principle of Capsicum Fruits.Part IX. (Received September 2, 1980; Accepted November 17, 1980)