Investigation of the electrophilic reactivity of the biologically active marine sesquiterpenoid onchidal and model compounds

• Melissa M. Cadelis and
• Brent R. Copp

Beilstein J. Org. Chem. 2018, 14, 2229–2235, doi:10.3762/bjoc.14.197

• Melissa M. Cadelis Brent R. Copp School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland 1142, New Zealand 10.3762/bjoc.14.197 Abstract The structure of the sesquiterpene onchidal (6), a component of the defensive secretion of the shell-less mollusc Onchidella binneyi

• , contains a masked α,β-unsaturated 1,4-dialdehyde moiety, the presence of which has been proposed to be the cause of the feeding deterrent activity exhibited by the mollusc. We have found onchidal acts as an electrophile, reacting rapidly with the model nucleophile n-pentylamine forming diastereomeric

• aminated pyrrole adducts. Somewhat surprisingly, no reaction was observed between onchidal and n-pentanethiol. Structurally simplified n-pentyl 11–13 and cyclohexylmethyl 15–17 analogues of onchidal were prepared and demonstrated similar amine-selective reactivity. Onchidal and analogues reacted with the