Enantioselective Addition of Allyltin Reagents to Amino Aldehydes Catalyzed with Bis(oxazolinyl)phenylrhodium(III) Aqua Complexes.docVIP

Molecules 2011, 16, 5387-5401; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Enantioselective Addition of Allyltin Reagents to Amino Aldehydes Catalyzed with Bis(oxazolinyl)phenylrhodium(III) Aqua Complexes Yukihiro Motoyama 1,*, Takatoshi Sakakura 2, Toshihide Takemoto 2, Kayoko Shimozono 2, Katsuyuki Aoki 2 and Hisao Nishiyama 3 1 Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan 2 School of Materials Science, Toyohashi University of Technology, Tempaku-cho, Toyohashi, Aichi 441-8580, Japan 3 Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan * Author to whom correspondence should be addressed; E-Mail: motoyama@cm.kyushu-u.ac.jp; Tel.: +81-92-583-7821; Fax: +81-92-583-7839. Received: 30 May 2011; in revised form: 20 June 2011 / Accepted: 23 June 2011 / Published: 27 June 2011 Abstract: Bis(oxazolinyl)phenylrhodium(III) aqua complexes, (Phebox)RhX2(H2O) [X = Cl, Br], were found to be efficient Lewis acid catalysts for the enantioselective addition of allyl- and methallyltributyltin reagents to amino aldehydes. The reactions proceed smoothly in the presence of 5–10 mol % of (Phebox)RhX2(H2O) complex at ambient temperature to give the corresponding amino alcohols with modest to good enantioselectivity (up to 94% ee). Keywords: allylation; amino aldehydes; Lewis acids; pincer ligands; rhodium 1. Introduction The development of enantioselective synthesis of chiral homoallylic alcohols containing amino- functional groups is of great importance to synthetic organic and medicinal chemistry. Despite much effort directed at enantioselective allylation of aldehydes [1-3], there are only a few systems for enantioselective allylation of amino aldehydes as substrates because the high coordination ability