2010 Fiscal Year Final Research Report

Development of the Formation of Enolate Controlled by Acid-base Bifunctional Organochalcogenide Catalysts

Research Project

Project/Area Number	20590021
Research Category	Grant-in-Aid for Scientific Research (C)
Allocation Type	Single-year Grants
Section	一般
Research Field	Chemical pharmacy
Research Institution	Kinjo Gakuin University
Principal Investigator	WATANABE Shinichi Kinjo Gakuin University, 薬学部, 准教授 (40275095)
Project Period (FY)	2008 – 2010
Keywords	不斉反応 / 光学活性スルフィド / 光学活性セレニド / 光学活性テルリド / オキシラン / シクロプロパン / アジリジン / セレノニウム塩
Research Abstract	Asymmetric cyclopropanation, epoxidation and aziridination catalyzed by chiral chalcogenides are described. A novel Lewis acid/Bronsted base catalysts formed by a C2 symmetric chiral chalcogenide bearing isoborneol or camphor skeletons were readily prepared from (1S)-10-camphorsulfonic acid. Di-exo-2-hydroxy-10- bornyl selenide and LiH promoted the reaction of phenacyl bromide with methyl vinyl ketone to afford the desired trans cyclopropane with up to 50% ee. The reaction of phenacyl bromide with N-benzylidene-4-methylbenzenesulfonamide was also catalyzed by the selenide to produce the cis aziridine with up to 60% ee. Although the good yields and moderate enantioselectivities for oxirane formations were obtained from the reaction of phenacyl bromide with aromatic aldehydes, the reactions with aliphatic aldehydes afforded the desired epoxides in good yields and poor enantioselectivities.

(3 results)