title: Memory of chirality generated by spontaneous crystallization and asymmetric synthesis using the frozen chirality.
abstract: Asymmetric synthesis using frozen chirality generated by spontaneous crystallization was performed. Achiral asymmetrically substituted imide with a tetrahydronaphthyl group on the nitrogen atom crystallized in a chiral fashion, with space group P2(1)2(1)2(1). The molecular chirality generated by spontaneous crystallization was retained in cold THF. The half-life determined on the basis of decreasing optical activity followed by CD spectrometer was 7.8, 33.1, and 150.0 min at -20, -30, -40 degrees C, respectively. The energy barrier (DeltaG()) of racemization was calculated with the temperature dependence of the kinetic constant to be 18.24-18.36 kcal mol(-)(1) at 233-253 K. The memorized frozen chirality was transferred to permanent optically active alcohols by nucleophilic addition with n-buthyllithium.
authors.affiliation: Department of Materials Technology, Faculty of Engineering, Chiba University, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan. sakamotom@faculty.chiba-u.ac.jp
authors.forename: Masami
authors.initials: M
authors.lastname: Sakamoto
authors.forename: Takuya
authors.initials: T
authors.lastname: Iwamoto
authors.forename: Naoyuki
authors.initials: N
authors.lastname: Nono
authors.forename: Masaru
authors.initials: M
authors.lastname: Ando
authors.forename: Wataru
authors.initials: W
authors.lastname: Arai
authors.forename: Takashi
authors.initials: T
authors.lastname: Mino
authors.forename: Tsutomu
authors.initials: T
authors.lastname: Fujita