Departamento de Química Orgánica I, Facultad de Química, Universidad del País Vasco, Apdo. 1072, 20080, San Sebastián, Spain.
J Org Chem. 2012 Jan 6;77(1):747-53. doi: 10.1021/jo202073n. Epub 2011 Dec 14.
The catalytic direct α-alkylation of aldehydes with 2-(bromomethyl)acrylates has been accomplished, giving rise to α-branched and functionalized aldehydes of high diastereo- and enantiopurity. The influence of the nature of the ester group of the acrylates in reaction stereoselectivity and especially in reactivity is investigated. Optimum conditions implicate the use of phenyl acrylates in conjunction with organocatalyst 8. Application of thus obtained adducts in synthesis is illustrated with a concise stereocontrolled preparation of trisubstituted cyclopentenes.
醛与 2-（溴甲基）丙烯酸酯的催化直接α-烷基化已经完成，得到高非对映和对映选择性的α-支化和官能化醛。研究了丙烯酸酯酯基的性质对反应立体选择性的影响，特别是对反应性的影响。最佳条件涉及使用苯基丙烯酸酯与有机催化剂 8 一起使用。通过简洁的立体控制制备三取代环戊烯说明了所得到的加合物在合成中的应用。
