General Synthetic Approach to Rotenoids via Stereospecific, Group-Selective 1,2-Rearrangement and Dual SNAr Cyclizations of Aryl Fluorides

Seiya Matsuoka; Kayo Nakamura; Ken Ohmori; Keisuke Suzuki

doi:10.1055/s-0037-1611654

Synthesis, Table of Contents

CC BY-ND-NC 4.0 · Synthesis 2019; 51(05): 1139-1156
DOI: 10.1055/s-0037-1611654

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General Synthetic Approach to Rotenoids via Stereospecific, Group-Selective 1,2-Rearrangement and Dual S_NAr Cyclizations of Aryl Fluorides

Seiya Matsuoka

,

Kayo Nakamura

,

Ken Ohmori *

,

Keisuke Suzuki *

Department of Chemistry, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8551, Japan Email: ksuzuki@chem.titech.ac.jp

› Author Affiliations

Abstract

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Dedicated to the memory of the late Professor Sho Ito

Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

A general synthetic approach to rotenoids is described, featuring 1) stereospecific, group-selective 1,2-rearrangements of epoxy alcohols, and 2) S_NAr oxy-cyclizations of aryl fluorides. The common intermediate epoxyketone, en route to (–)-rotenone and (–)-deguelin, was prepared from d-araboascorbic acid in five steps. Also described is the conversion of (–)-deguelin into oxidized congeners, (–)-tephrosin and (+)-12a-epi-tephrosin.

Key words

isoflavonoid - rotenoid - semi-pinacol rearrangement - S_NAr cyclization - total synthesis

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References

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