| Title: | Structural verification of petromyzestrosterol by total syntheses of both C14-epimers of its 3-O-methyl derivative |
| Author(s): | Nakazaki A; Kawai M; Nishikawa T; |
| Address: | "Graduate School of Bioagricultural Sciences, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8601, Japan. Faculty of Science and Engineering, Iwate University, Ueda, Morioka 020-8551, Japan. nakazaki@iwate-u.ac.jp" |
| ISSN/ISBN: | 1477-0539 (Electronic) 1477-0520 (Linking) |
| Abstract: | "The structure of petromyzestrosterol, a pheromonal steroid of the sea lamprey, was verified by total syntheses of both C14-epimers of its 3-O-methyl derivative. The key features of our synthesis involve (1) a highly stereoselective Mizoroki-Heck reaction to unite the A- and CD-ring segments and (2) Friedel-Crafts-type cyclodehydration to construct the B-ring. Petromyzestrosterol is concluded to bear an alpha-configured C14 hydroxy group based on a comparison of NMR data of both the synthesized C14-epimers of the 3-O-methyl derivative with those of the natural petromyzestrosterol. The downfield shifts of C9 and C12 via the gamma-gauche effect in the 14beta-isomer would enable the structural elucidation of C14 in the 14-hydroxy estrogenic steroids" |
| Keywords: | Isomerism Magnetic Resonance Spectroscopy *Steroids/chemistry; |
| Notes: | "MedlineNakazaki, Atsuo Kawai, Maho Nishikawa, Toshio eng Research Support, Non-U.S. Gov't England 2022/07/27 Org Biomol Chem. 2022 Aug 17; 20(32):6432-6435. doi: 10.1039/d2ob01047j" |
