Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, Sendai 981-8558, Japan.
Org Biomol Chem. 2014 Mar 28;12(12):1983-94. doi: 10.1039/c3ob42229a. Epub 2014 Feb 19.
Intramolecular iridium-catalyzed allylic aminations of homochiral (E)-6-N-nosylaminohept-2-en-1-yl methyl carbonates were investigated. The relative position of the 2,5-substituents of the resulting pyrrolidines was found to be controlled by using both enantiomers (4 and 5) of the appropriate chiral ligand, demonstrating a simple and highly stereodivergent synthetic protocol. Selected trans- and cis-2,5-disubstituted 3-hydroxypyrrolidines (2a and 18a) were converted to (+)-bulgecinine (6) and (+)-preussin (7), respectively.
手性（E）-6-N-硝磺酰氨基庚-2-烯-1-基甲基碳酸酯的分子内铱催化烯丙基胺化反应得到了研究。通过使用合适手性配体的两种对映异构体（4 和 5），发现所得吡咯烷的 2,5-取代基的相对位置得到控制，展示了一种简单且高度立体发散的合成方案。选择的反式和顺式 2,5-二取代 3-羟基吡咯烷（2a 和 18a）分别转化为（+）- bulgecinine（6）和（+）- preussin（7）。
