Semisynthesis of Linariophyllenes A–C and Rumphellolide H, Structure Revisions and Proposed Biosynthesis Pathways
able S1. NMR spectroscopic data for isokobusone ( 9 ) ................................ ................................ .............. S 4 Table S2. NMR spectroscopic data for linariophyllene B ( 2 ) ................................ ................................ ...... S 5 Table S3. NMR spectroscopic data for linariophyllene A ( 14 ) ................................ ................................ .... S 6 Table S4. NMR spectroscopic data for disproved structure of linariophyllene C ( 3 ) ................................ .. S 7 Table S5. NMR spectroscopic data for revised structure of linariophyllene C ( 31 ) ................................ .... S 8 Table S6. NMR spectroscopic data for rumphellolide H ( 4 ) ................................ ................................ ....... S 9 Table S7. Comparison of NMR data of isolated and synthesized isokobusone ( 9 ) ................................ ... S 10 Table S8. Comparison of NMR data of isolated and synthesized linariophyllene B ( 2 ) ........................... S 11 Table S9. Comparison of NMR data of isolated and synthesized linariophyllene A ( 14 ) ......................... S 12 Table S10. Comparison of NMR shifts between proposed structure of linariophyllene C ( 3 ), corresponding natural isolate, and revised structure of linariophyllene C ( 31 ) ................................ ................................ .. S 13 Table S11. Comparison of NMR data of isolated and synthesized rumphellolide H ( 4 ) ........................... S 14 Table S12 . Comparison of specific rotation data ................................ ................................ ....................... S 15 NMR spectra of isolated compounds ................................ ................................ ................................ ...... S 16 S1. NMR spectra of epoxydiol 7 ................................ ................................ ................................ ................ S 16 S2. NMR spectra of kobusone ( 8 ) ................................ ................................ ................................ .............. S 18 S3. NMR spectra of isokobusone ( 9 ) ................................ ................................ ................................ .......... S 20 S4. NMR spectra of silyl ether 10 ................................ ................................ ................................ .............. S 26 S5. NMR spectra of diol 12 ................................ ................................ ................................ ........................ S 29 S6. NMR spectra of linariophyllene B ( 2 ) ................................ ................................ ................................ .. S 31 S7. NMR spectra of silyl ether 13 ................................ ................................ ................................ .............. S 37 S8. NMR spectra of linariophyllene A ( 14 ) ................................ ................................ ................................ S 39 S9. NMR spectra of allylic alcohol 15 ................................ ................................ ................................ ........ S 45 S10. NMR spectra of epoxyalcohol 16 ................................ ................................ ................................ ....... S 47 S11. NMR spectra of epoxyalcohol 17 ................................ ................................ ................................ ....... S 50 S12. NMR spectra of methanesulfonate 18 ................................ ................................ ................................ S 52 S13. NMR spectra of isocaryophyllene - 4 S , 5 R - oxide ( 19 ) ................................ ................................ .......... S 54 S14. NMR spectra of disproved structure of linariophyllene C ( 3 ) ................................ ............................ S 56 S15. NMR spectra of mixture of epoxyacetate 20 and tetrahydrofuran 21 ( 20 : 21 = 2.2 : 1) ................... S 62 S16. NMR spectra of acetate 22 ................................ ................................ ................................ ................. S 68 S17. NMR spectra of diol 23 ................................ ................................ ................................ ...................... S 70 S18. NMR spectra of isocaryophyllene - 4 R , 5 S - oxide ( 24) ................................ ................................ .......... S 72 S19. NMR spectra of acetate 27 ................................ ................................ ................................ ................. S 74 S 3 S20. NMR spectra of tetrahydrofuran 28 ................................ ................................ ................................ ... S 76 S21. NMR spectra of diepoxide 29 ................................ ................................ ................................ ............ S 82 S22. NMR spectra of epoxydiol 30 ................................ ................................ ................................ ............ S 84 S23. NMR spectra of linariophyllene C ( 31 ) ................................ ................................ .............................. S 86 S24. NMR spectra of rumphellolide H ( 4 ) ................................ ................................ ................................ . S 92 IR spectra of synthesized compounds ................................ ................................ ................................ ..... S 98 X - Ray crystallographic supplementary data for compound 7 ................................ ............................ S 119 X - Ray crystallographic supplementary data for isokobusone (9) ................................ ...................... S 121 X - Ray crystallographic supplementary data for linariophyllene B (2) ................................ .............. S 123 X - Ray crystallographic supplementary data for linariophyllene A (14) ................................ ........... S 125 X - Ray crystallographic supplementary data for disproved structure of linariophyllene C (3) ....... S 127 X - Ray crystallographic supplementary data for epoxyacetate 22 ................................ ...................... S 129 X - Ray crystallographic supplementary data for epoxyacetate 27 ................................ ...................... S 131 X - Ray crystallographic supplementary data for diepoxide 29 ................................ ........................... S 133 X - Ray crystallographic supplementary data for linariophyllene C (31) ................................ ........... S 135 X - Ray crystallographic supplementary data for rumphellolide H (4) ................................ ............... S 137
Pieteikuma datums
01.10.2023.
Atslēgas vārdi
Chemical structure,Diols,Mixtures,Molecular structure,Solution chemistry
Hipersaite
https://pubs.acs.org/doi/10.1021/acs.jnatprod.3c00574?goto=supporting-info
