Vilaivan Tirayut, Winotapan Chutima, Banphavichit Vorawit, Shinada Tetsuro, Ohfune Yasufumi
Organic Synthesis Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Patumwan, Bangkok 10330, Thailand.
J Org Chem. 2005 Apr 29;70(9):3464-71. doi: 10.1021/jo0477244.
[reaction: see text] Chiral aldimines derived from phenylglycinol were diastereoselectively allylated with indium powder/allyl bromide in alcoholic solvents. Both aliphatic and aromatic aldimines provided good yield of the desired products with high diastereoselectivity. A racemization-free protocol for removal of the phenylglycinol auxiliary was also developed. The stereochemical assignment of the homoallylic amine was made by NMR spectroscopy and a transition state model was proposed to explain the selectivity.
[反应：见正文] 由苯甘醇衍生的手性醛亚胺在醇类溶剂中用铟粉/烯丙基溴进行非对映选择性烯丙基化反应。脂肪族和芳香族醛亚胺均以高非对映选择性提供了高产率的所需产物。还开发了一种无消旋化的方法来去除苯甘醇辅助基团。通过核磁共振光谱对高烯丙基胺进行了立体化学归属，并提出了一个过渡态模型来解释选择性。
