Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, IN, 47405, USA.
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, Republic of Korea.
Angew Chem Int Ed Engl. 2019 Feb 4;58(6):1727-1731. doi: 10.1002/anie.201812894. Epub 2019 Jan 15.
The direct, catalytic substitution of unactivated alcohols remains an undeveloped area of organic synthesis. Moreover, catalytic activation of this difficult electrophile with predictable stereo-outcomes presents an even more formidable challenge. Described herein is a simple iron-based catalyst system which provides the mild, direct conversion of secondary and tertiary alcohols to sulfonamides. Starting from enantioenriched alcohols, the intramolecular variant proceeds with stereoinversion to produce enantioenriched 2- and 2,2-subsituted pyrrolidines and indolines, without prior derivatization of the alcohol or solvolytic conditions.
未活化的醇的直接催化取代仍然是有机合成中一个未开发的领域。此外，用可预测的立体产物催化活化这种难处理的亲电试剂更是一个艰巨的挑战。本文描述了一种简单的铁基催化剂体系，该体系可温和、直接地将仲醇和叔醇转化为磺酰胺。从对映体富集的醇开始，分子内变体进行立体反转生成对映体富集的 2-和 2,2-取代的吡咯烷和吲哚啉，而无需醇的预先衍生化或溶剂解条件。
