title: Unusual reversal of enantioselectivity in the asymmetric autocatalysis of pyrimidyl alkanol triggered by chiral aromatic alkanols and amines.
abstract: Temperature dependent inversion of enantioselectivity in asymmetric catalysis is an interesting and somewhat unusual phenomenon. We have observed temperature dependent inversion of enantioselectivity in the asymmetric autocatalysis reaction when triggered by a wide scope of enantioenriched alcohols and amines. The addition reaction of diisopropylzinc to pyrimidine-5-carbaldehyde in the presence of enantiopure alcohols or amines affords the pyrimidyl alkanol product at 0 °C with high ee. However, lowering the reaction temperature to -44 °C affords the opposite enantioselectivity.
authors.affiliation: Department of Applied Chemistry, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan. soai@rs.kagu.tus.ac.jp and Research Center for Chirality, Research Institute for Science and Technology, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
authors.forename: Arimasa
authors.initials: A
authors.lastname: Matusmoto
authors.affiliation: Department of Applied Chemistry, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan. soai@rs.kagu.tus.ac.jp.
authors.forename: Satoshi
authors.initials: S
authors.lastname: Fujiwara
authors.affiliation: Department of Applied Chemistry, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan. soai@rs.kagu.tus.ac.jp.
authors.forename: Yui
authors.initials: Y
authors.lastname: Hiyoshi
authors.affiliation: Department of Process Research & Development, Merck Research Laboratories, Rahway, NJ, USA.
authors.forename: Kerstin
authors.initials: K
authors.lastname: Zawatzky
authors.affiliation: Department of Process Research & Development, Merck Research Laboratories, Rahway, NJ, USA.
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Makarov
authors.affiliation: Department of Process Research & Development, Merck Research Laboratories, Rahway, NJ, USA.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Welch
authors.affiliation: Department of Applied Chemistry, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan. soai@rs.kagu.tus.ac.jp and Research Center for Chirality, Research Institute for Science and Technology, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
authors.forename: Kenso
authors.identifier: http://orcid.org/0000-0002-8060-444X
authors.initials: K
authors.lastname: Soai