An Unusual Terpene Cyclization Mechanism Involving a Carbon–Carbon Bond Rearrangement (pages 4353–4356)
Dr. Ayuko Meguro, Yudai Motoyoshi, Kazuya Teramoto, Shota Ueda, Yusuke Totsuka, Yumi Ando, Dr. Takeo Tomita, Dr. Seung-Young Kim, Dr. Tomoyuki Kimura, Dr. Masayuki Igarashi, Dr. Ryuichi Sawa, Prof. Dr. Tetsuro Shinada, Prof. Dr. Makoto Nishiyama and Prof. Dr. Tomohisa Kuzuyama
Article first published online: 16 FEB 2015 | DOI: 10.1002/anie.201411923
Biosynthetic virtuosity: Cyclooctat-9-en-7-ol synthase (CotB2) catalyzes the synthesis of an unusual 5-8-5 fused-ring structure with six chiral centers from the achiral C20 substrate geranylgeranyl diphosphate. By combining in vivo studies with in vitro reactions, an unusual cyclization mechanism was elucidated, which involves a carbon–carbon backbone rearrangement and three long-range hydride shifts. OPP=pyrophosphate.