Synthesis of the Spirocyclic Imine Fragment of Portimines Using a γ-Hydroxymethyl-α , β-butenolide Dienophile in a Diastereoselective Diels-Alder Reaction

Ze Kuang; Xiao-Bo Ding; Freda F Li; Margaret A Brimble

doi:10.1021/acsomega.4c08699

Synthesis of the Spirocyclic Imine Fragment of Portimines Using a γ-Hydroxymethyl-α , β-butenolide Dienophile in a Diastereoselective Diels-Alder Reaction

ACS Omega. 2024 Oct 31;9(45):45624-45632. doi: 10.1021/acsomega.4c08699. eCollection 2024 Nov 12.

Authors

Ze Kuang¹, Xiao-Bo Ding^{1

2}, Freda F Li^{1

2}, Margaret A Brimble^{1

2}

Affiliations

¹ School of Chemical Sciences, The University of Auckland, 23 Symonds Street, Auckland 1010, New Zealand.
² The Maurice Wilkins Centre for Molecular Biodiscovery, The University of Auckland, 3 Symonds Street, Auckland 1010, New Zealand.

Abstract

The synthesis of the spirocyclic imine fragment of the portimine family of marine toxins has been achieved. A densely functionalized key lactone-ester intermediate was assembled via a highly diastereoselective Diels-Alder cycloaddition, involving a novel γ-hydroxymethyl-α,β-butenolide dienophile. A Stille coupling was employed to install the vinyl group. Selective elaboration of the two carbonyl groups successfully afforded the spirocyclic imine fragment.