The relative configurations around the bis-THF rings were determined by analysis of the 1H NMR spectrum and
comparison with literature data. In Figure S3a, the chemical shifts atδH 3.39 (H-21) and 3.84 (H-20) indicated the S* and S* relative configurations, while the S* and R* relative configurations were deduced for C-12 and C-13 and for C-16 and C-17, due to the similarity of the chemical shift of H-12 (δH3.87) and H-13 (δH3.83) and that of H-16 (δH3.93) and H-17 (δH3.91).17,18The methylene protons H-18 and H-19 were assigned to signals at δH1.60 and 1.97 on the basis of COSY correlations between H-20 and H-21, H-19 and H-20,and H-18 and H-17, combined with HMBC coupling between H-19 and C-17. The difference between these chemical shifts indicated a trans configuration for the C-17/C-20 THF ring.19In the same manner, a trans configuration was assigned to the C-13/C-16 THF ring based on the divergent chemical shifts atδH1.62 and 1.87 for H-14 and H-15.19Thus, the relative configuration around the bis-THF rings was concluded to be S*, R*, R*, S*, S*, S* for C-12, C-13, C-16, C-17, C-20, and C-21. The absolute configuration of C-36 was determined by CD spectroscopic analysis. The negative n−π* Cotton effect (Δε =−1.13) at 238 nm and a positive π−π* Cotton effect (Δε =8.79) at 208 nm clearly indicated the S configuration at C-36 in the lactone ring.16The absolute configurations of the OH groups adjacent to the THF rings were determined by Mosher ester methodology20 using the (R)-MPA and (S)-MPA derivatives21 and the “in NMR tube” method.22As shown in Figure S4a, the ΔδH(=δS− δR) was negative on both chain sides and positive along the THF rings, indicating S configurations at both C-12 and C-21.23The configuration of C-8 could not be determined due to the negative ΔδH values displayed by both H-7 and H-9 on the hydrocarbon chain.