title: Use of a Catalytic Chiral Leaving Group for Asymmetric Substitutions at sp3-Hybridized Carbon Atoms: Kinetic Resolution of β-Amino Alcohols by p-Methoxybenzylation.
abstract: A catalytic strategy was developed for asymmetric substitution reactions at sp3-hybridized carbon atoms by using a chiral alkylating agent generated in situ from trichloroacetimidate and a chiral phosphoric acid. The resulting chiral p-methoxybenzyl phosphate selectively reacts with β-amino alcohols rather than those without a β-NH functionality. The use of an electronically and sterically tuned chiral phosphoric acid enables the kinetic resolution of amino alcohols through p-methoxybenzylation with good enantioselectivity.
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan.
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Kuroda
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan.
authors.forename: Shingo
authors.initials: S
authors.lastname: Harada
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan.
authors.forename: Akinori
authors.initials: A
authors.lastname: Oonishi
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan.
authors.forename: Hiroki
authors.initials: H
authors.lastname: Kiyama
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan.
authors.forename: Yousuke
authors.initials: Y
authors.lastname: Yamaoka
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan. yamak@tokushima-u.ac.jp.|Graduate School of Pharmaceutical Sciences, Tokushima University, Shomachi, Tokushima, 770-8505, Japan. yamak@tokushima-u.ac.jp.
authors.forename: Ken-Ichi
authors.initials: KI
authors.lastname: Yamada
authors.affiliation: Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8501, Japan. kay-t@pharm.kyoto-u.ac.jp.
authors.forename: Kiyosei
authors.initials: K
authors.lastname: Takasu
keywords: Brønsted acid catalysis; asymmetric catalysis; kinetic resolution; substitution reactions; β-amino alcohols