Hatano Manabu, Okamoto Haruka, Kawakami Taro, Toh Kohei, Nakatsuji Hidefumi, Sakakura Akira, Ishihara Kazuaki
Graduate School of Engineering , Nagoya University , Furo-cho, Chikusa , Nagoya 464-8603 , Japan . Email:
Graduate School of Natural Science and Technology , Okayama University , 3-1-1 Tsushimanaka, Kita-ku , Okayama 700-8530 , Japan . Email:
Chem Sci. 2018 Jun 25;9(30):6361-6367. doi: 10.1039/c8sc02290a. eCollection 2018 Aug 14.
Chiral - and -symmetric BINOL-derived bis(phosphoric acid) catalysts, which have OP([double bond, length as m-dash]O)(OH)/OP([double bond, length as m-dash]O)(OH)(OR) moieties at the 2,2'-positions, were developed and used for the enantioselective aza-Friedel-Crafts reaction of 2-methoxyfuran with α-ketimino esters for the first time. The intramolecular conjugated double hydrogen bond network is a key to increasing the Brønsted acidity and preventing deactivation of the catalysts. Highly functionalized α-amino acid derivatives with a chiral quaternary carbon center could be transformed into versatile optically active - and -heterocycles and an α-aryl-substituted serine.
首次开发了在2,2'-位具有OP（=O）（OH）/OP（=O）（OH）（OR）部分的手性和对称联萘衍生的双（磷酸）催化剂，并将其用于2-甲氧基呋喃与α-酮亚胺酯的对映选择性氮杂傅克反应。分子内共轭双氢键网络是提高布朗斯特酸度和防止催化剂失活的关键。具有手性季碳中心的高度官能化α-氨基酸衍生物可以转化为通用的光学活性杂环和α-芳基取代的丝氨酸。
