Departamento de Quı́mica Orgánica, Facultad de Ciencias and Instituto de Sı́ntesis Orgánica (ISO), Universidad de Alicante , Apdo. 99, 03080 Alicante, Spain.
J Org Chem. 2014 Feb 21;79(4):1796-804. doi: 10.1021/jo402854z. Epub 2014 Feb 6.
A simple and robust protocol is detailed for the preparation of enantioenriched α-substituted (1,4-pentadien-3-yl)amine derivatives. The methodology involves the addition of an in situ formed pentadienyl indium reagent to chiral tert-butylsulfinimines, previously formed in the same pot. The addition takes place with excellent γ-regio- and diastereoselectivity for a wide range of carbonyl compounds, including α-unsubstituted aldehydes and methyl alkyl ketones. The catalytic hydrogenation of the sulfinamines obtained provides a convenient access to chiral α-substituted (3-pentyl)amines. The hydroboration-oxidation of the α-(1,4-pentadien-3-yl)amine derivatives, followed by a cyclization under Mitsunobu conditions, takes place with an excellent diastereoselectivity governed by the chiral sulfinyl group.
本文详细介绍了一种简单而稳健的方法，用于制备对映体富集的α-取代（1,4-戊二烯-3-基）胺衍生物。该方法涉及在同一锅中形成的手性叔丁基亚磺亚胺的原位形成的戊二烯基铟试剂的加成。该加成反应对包括α-未取代的醛和甲基烷基酮在内的各种羰基化合物具有优异的γ-区域和立体选择性。所得到的亚磺酰胺的催化氢化提供了一种方便的方法来获得手性α-取代的（3-戊基）胺。α-（1,4-戊二烯-3-基）胺衍生物的硼氢化-氧化，然后在 Mitsunobu 条件下环化，在手性亚磺酰基的控制下具有优异的立体选择性。
