Stereoselective construction of three- and four-contiguous asymmetric centers: Novel possibility by alkylative rearrangement of epoxy silyl ethers
✍ Scribed by Masato Shimazaki; Munetsugu Morimoto; Keisuke Suzuki
- Publisher
- Elsevier Science
- Year
- 1990
- Tongue
- French
- Weight
- 255 KB
- Volume
- 31
- Category
- Article
- ISSN
- 0040-4039
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✦ Synopsis
Stereospecific 1,2-marrsngernent of epoxy silyl etbers in the presence of nucleophiles is desuibed. The reaction affords 19diols or cormspond@ mono-silylated ethers. which prwides a route to establish three-or four-cootiguons asymmetric centers io one step.
Previously, we reported a stereoselective synthetic method of 2-vinyl-19diols which are versatile in natural product synthesis.
The method depends on the rearrangement-reduction sequence (Scheme l), starting from epoxy trimethylsilyl (TMS) ether 1.1) The Th4!%inyl group serves not only as a good migrating group in the 1,2rearrangement (step 1) but also as a controlling element for dictating the hydride attack to 2 (step 2). Large steric bias posed by this group leads to highly selective formation of &&y&i01 3 (see model I).