Stereocontrolled synthesis of the aminocyclitol moiety of (+)-trehazolin via C-H insertion reaction of alkylidenecarbene.

Akiyama, Megumi; Awamura, Toshiki; Kimura, Kazuhito; Hosomi, Yoshimi; Kobayashi, Ayako; Tsuji, Kazutaka; Kuboki, Atsuhito; Ohira, Susumu.

(±)-Me (2Z,6R*,8R*,9E)-3,6-epoxy-4,6,8-triethyl-2,4,9-dodecatrienoate (I), a major metabolite of the Caribbean sponge, was synthesized in a stereocontrolled manner from γ-caprolactone. The key step was one-pot generation of alkylidenecarbenes at two sites followed by 1,2 hydride shift and intramol. 1,5 C-H insertion.

Tetrahedron Letters

Elsevier B.V.

45

38

7133

7136