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Enantiocontrol by assembled attractive interactions in copper-catalyzed asymmetric direct alkynylation of alpha-ketoesters with terminal alkynes: OH center dot center dot center dot O/sp(3)-CH center dot center dot center dot O two-point hydrogen bonding
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| Title: | Enantiocontrol by assembled attractive interactions in copper-catalyzed asymmetric direct alkynylation of alpha-ketoesters with terminal alkynes: OH center dot center dot center dot O/sp(3)-CH center dot center dot center dot O two-point hydrogen bonding |
| Authors: | Schwarzer, Martin C. Browse this author | | Fujioka, Akane Browse this author | | Ishii, Takaoki Browse this author | | Ohmiya, Hirohisa Browse this author →KAKEN DB | | Mori, Seiji Browse this author | | Sawamura, Masaya Browse this author →KAKEN DB |
| Issue Date: | 14-Apr-2018 |
| Publisher: | Royal Society of Chemistry |
| Journal Title: | Chemical science |
| Volume: | 9 |
| Issue: | 14 |
| Start Page: | 3484 |
| End Page: | 3493 |
| Publisher DOI: | 10.1039/c8sc00527c |
| Abstract: | Copper-catalyzed asymmetric direct alkynylation of alpha-ketoesters with terminal alkynes with chiral prolinol-phosphine ligands, most preferably (alpha R, 2S)-1-(2-dicyclohexylphosphinobenzyl)-alpha-neopentyl-2-pyrrolidinemethanol, afforded various enantioenriched chiral propargylic tertiary alcohols. Quantumchemical calculations using the BP86 density functional including Grimme's empirical dispersion correction [DF-BP86-D3(BJ)-PCM(tBuOH)/TZVPP//DF-BP86-D3(BJ)/SVP] show the occurrence of OH center dot center dot center dot O/sp(3)-CH center dot center dot center dot O two-point hydrogen bonding between the chiral ligand and the carbonyl group of the ketoester in the stereo-determining transition states. Combined with the hydrogen-bonding interactions orienting the ketoester substrate, dispersive attractions between the chiral ligand (P-cyclohexyl groups) and the ketoester in the favored transition states, rather than steric repulsions in the disfavored transition state explain the enantioselectivity of the asymmetric copper catalysis. |
| Rights: | https://creativecommons.org/licenses/by/3.0/ |
| Type: | article |
| URI: | http://hdl.handle.net/2115/70706 |
| Appears in Collections: | 理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 澤村 正也
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