Tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP) Efficient Catalysts for the Cyanosilylation and Cyanocarbonation of Aldehydes and Ketones 英文参考文献.docVIP

Molecules 2009, 14, 3353-3359; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP): Efficient Catalysts for the Cyanosilylation and Cyanocarbonation of Aldehydes and Ketones Satoru Matsukawa *, Izumi Sekine and Ayumi Iitsuka Department of Science Education, Faculty of Education, Ibaraki University, Ibaraki, 310-8512 Japan * Author to whom correspondence should be addressed; E-mail: smatsuka@mx.ibaraki.ac.jp; Fax: +81292288234. Received: 6 August 2009; in revised form: 25 August 2009 / Accepted: 31 August 2009 / Published: 2 September 2009 Abstract: A variety of aldehydes and ketones were transformed to their corresponding cyanohydrin silyl ethers in good to excellent yields in the presence of 1-5 mol% of tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP). Cyanohydrin carbonates were also readily prepared using 5-10 mol% of TTMPP as an organocatalyst. Keywords: organocatalysis; cyanosilylaton; cyanohydrin carbonate; phosphines; cyanation Introduction The addition of trimethylsilyl cyanide (TMSCN) to carbonyl compounds is one of the most popular strategies to afford cyanohydrins, which can be conveniently converted into various important polyfunctionalized building blocks for the synthesis of many natural products and bioactive molecules, including α-hydroxyl carbonyl compounds and β-amino alcohols [1-7]. Consequently, many catalytic systems, such as metal salts, organocatalysts, inorganic solid acids and bases, have been developed to enhance the efficiency of this transformation. Organophosphorous compounds have also been employed. Mukaiyama reported that Bu3P and Ph3P act as catalysts for the cyanosilylation with aldehydes [8]. Plumet [9,10] and Tian [11] independently reported that phosphonium salts-catalyzed cyanosilylation with aldehydes and ketones. Verkade’s base (cyclo