化学选择性和对映选择性的银催化内分子氮丙啶化反应。
Chemo- and Enantioselective Intramolecular Silver-Catalyzed Aziridinations.
机构信息
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, 53706, USA.
出版信息
Angew Chem Int Ed Engl. 2017 Aug 7;56(33):9944-9948. doi: 10.1002/anie.201704786. Epub 2017 Jul 12.
Abstract
Asymmetric nitrene-transfer reactions are a powerful tool for the preparation of enantioenriched amine building blocks. Reported herein are chemo- and enantioselective silver-catalyzed aminations which transform di- and trisubstituted homoallylic carbamates into [4.1.0]-carbamate-tethered aziridines in good yields and with ee values of up to 92 %. The effects of the substrate, silver counteranion, ligand, solvent, and temperature on both the chemoselectivity and ee value were explored. Stereochemical models were proposed to rationalize the observed absolute stereochemistry of the aziridines, which undergo nucleophilic ring opening to yield enantioenriched amines with no erosion in stereochemical integrity.
摘要
不对称氮烯转移反应是制备手性胺砌块的有力工具。本文报道了银催化的化学选择性和对映选择性胺化反应，可将二取代和三取代的偕丙基氨基甲酸酯转化为[4.1.0]-氨基甲酸酯桥联氮丙啶，收率高，ee 值高达 92%。考察了底物、银反离子、配体、溶剂和温度对化学选择性和 ee 值的影响。提出了立体化学模型来合理推断氮丙啶的绝对立体化学，氮丙啶经亲核开环反应生成手性胺，立体化学完整性没有损失。
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