SiMe3-based homologation-epoxidation-cyclization strategy for ladder THP synthesis.
A trimethylsilyl (SiMe(3)) group is the basis of a strategy that emulates the three fundamental proposed processes in ladder polyether biosynthesis: chain homologation, stereoselective epoxidation (>95% ee or >95:5 dr), and endo-selective, stereospecific (inversion) hydroxyepoxide cyclization (>95:5 endo:exo, >95% dr). A tris-THP was synthesized in 18 total operations from commercial materials using this approach. [reaction: see text]
Heffron
Timothy P
TP
Massachusetts Institute of Technology, Department of Chemistry, Cambridge, MA 02139, USA.
Jamison
Timothy F
TF
D003500:Cyclization; D004852:Epoxy Compounds / Q000737:chemistry*; D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D011714:Pyrans / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
D004852:Epoxy Compounds; D004987:Ethers; D011714:Pyrans; D014297:Trimethylsilyl Compounds