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Direct enantio-convergent transformation of racemic substrates without racemization or symmetrization
| Title: | Direct enantio-convergent transformation of racemic substrates without racemization or symmetrization |
| Authors: | Ito, Hajime Browse this author | | Kunii, Shun Browse this author | | Sawamura, Masaya Browse this author |
| Issue Date: | Nov-2010 |
| Publisher: | Nature Publishing Group |
| Journal Title: | Nature Chemistry |
| Volume: | 2 |
| Issue: | 11 |
| Start Page: | 972 |
| End Page: | 976 |
| Publisher DOI: | 10.1038/NCHEM.801 |
| PMID: | 20966955 |
| Abstract: | Asymmetric reactions that transform racemic mixtures into enantio-enriched products are in high demand, however, classical kinetic resolution (KR) can afford enantiopure compounds in <50% yield even in an ideal case. Many deracemization processes thus have been developed including dynamic kinetic resolution (DKR) and dynamic kinetic asymmetric transformation (DYKAT), which can provide enantio-enriched products even after complete conversion of the racemic starting materials; however, these dynamic processes require racemization or symmetrization of the substrates or intermediates. We demonstrate a first chemical direct enantio-convergent transformation without racemization or symmetrization process. The copper(I)-catalysed asymmetric allylic substitution of a racemic allyl ethers afforded a single enantiomer of an α-chiral allylboronates with complete conversion and high enantioselectivity (up to 98% ee); one enantiomer of the substrate undergoes an anti-SN2'-type reaction whereas the other enantiomer reacts via a syn-SN2' pathway. The products, α-chiral allylboronates, cannot be prepared by dynamic procedures, were used in construction of all-carbon quaternary stereocentres. |
| Type: | article (author version) |
| URI: | http://hdl.handle.net/2115/45373 |
| Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 伊藤 肇
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