Unusual tigliane diterpenes from euphorbia grandicornis

Phytochemical study of the aerial parts of Euphorbia grandicornis led to the isolation of two new tigliane diterpenes, 16-angeloyloxy-13α-isobutanoyloxy-4β,9α,20-trihydroxytiglia-1,5-diene-3,7-dione (1) and 16-angeloyloxy-13α-isobutanoyloxy-4β,9α,7β-trihydroxytiglia-1,5-dien-3-one (2). The structures and relative configuration of the new compounds were elucidated on the basis of extensive spectroscopic analysis, including 1D and 2D NMR experiments (1H NMR, JMOD, 1H−1H COSY, NOESY, HSQC, and HMBC), mass spectrometry, and comparison with literature data. The biogenesis of 1 and 2 with respect to the unusual 5-en-7-one and 5-en-7-ol moieties is also discussed.