Synthesis of an Oxaspirolactone Intermediate for the Synthesis of Spirolides

Abstract

A new method has been established for the preparation of C 2-oxidized 5,5-spiroacetals, which are key intermediates for the synthesis of the bis-spiroacetal moiety of the spirolides. A bridged orthoester was used as a masked carboxylic acid in the preparation of these bicyclic oxaspirolactones. The synthesis of chiral lactone (12), a building block for the synthesis of the spirolides, is also reported. The two chiral centres in lactone (12) were assembled by addition of a chiral crotyl borane to an aldehyde. The structure of lactone (12) was determined by single-crystal X-ray diffraction; orthorhombic space group P2₁2₁2₁ (No. 19), a 12.437(2), b 23.881(4), c 7.545(1) Å, V 2240.9(5) ų, R(F) 0.0460, and R_w(F) 0.0458.