- A stereo- and enantioselective approach to clavulones from tricyclodecadienone using flash vacuum thermolysis
-
The stereo- and enantioselective synthesis of clavulones 6 and their analogues 48 is described. γ-Hydroxycyclopentenones (-)-13 and 44, which are key intermediates in this approach, are obtained from enantiopure endo-tricyclo[5.2.1.02,6]decadienones (+)-14 and (+)-20 in 6 and 8 steps, respectively. Crucial steps are the reductive epoxy ring opening in compounds (+)-25 and 39 to give the corresponding diols (+)-27 and 40, and the thermal cycloreversion of tricyclodecenones (+)-27 and 41, using the technique of flash vacuum thermolysis (FVT). The synthesis of enantiopure (-)-13 represents a formal total synthesis of clavulones 6. The synthesis of vlavulone analogues (-)-48E and (-)-48Z (X = CH2OH) is completed by condensation of 44 with aldehyde 45 followed by elimination of water and removal of the protective THP-group.
- Zhu, Jie,Yang, Ji-Ying,Klunder, Antonius J. H.,Liu, Zhi-Yu,Zwanenburg, Binne
-
-
Read Online
- TOTAL SYNTHESIS OF MARINE PROSTANOIDS CLAVULONES
-
An enantioselective and stereoselective synthesis of novel marine prostanoids clavulone II (1) and 12-O-desacetylclavulone II (2) has been accomplished.
- Nagaoka, Hiroto,Miyakoshi, Tohru,Yamada, Yasuji
-
p. 3621 - 3624
(2007/10/02)
-