Polyacetate-type and acetate-propionate hybrid-type polyketide skeletons have been constructed by the remote asymmetric induction of the vinylogous Mukaiyama aldol reactions using chiral oxazolidinone-attached vinylketene silyl N,O-acetals. In the acetate-propionate hybrid-type reaction, anti- and syn-adducts were selectively afforded using aldehydes and acetals, respectively. Therefore, in conjunction with the previously reported polypropionate-type reaction, all types of polyketide skeletons have been able to be synthesized. In addition to the transition states of the acetate-propionate hybrid-type reactions, difference of the stereo-control systems between the polyacetate-type reaction and the polypropionate-type reaction is discussed. Interestingly, in polyacetate-type and acetate-propionate hybrid-type reactions, the chiral auxiliary controlled the stereoselectivity indirectly. Additionally, (S)-massoialactone (α,β-unsaturated δ-lactone) and tabtoxinine-β-lactam, an inhibitor of glutamate synthetase, were synthesized by the remote asymmetric induction reactions.
|Translated title of the contribution||Synthesis of poly acetate and acetate-propionate hybrid-type polyketides using novel remote asymmetric induction reactions|
|Number of pages||11|
|Journal||Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry|
|Publication status||Published - 2021 Feb 1|
ASJC Scopus subject areas
- Organic Chemistry