Centre de Recherche de Gif-sur-Yvette, Institut de Chimie des Substances Naturelles, UPR 2301 CNRS, Avenue de la Terrasse, 91198 Gif-sur-Yvette, France.
J Org Chem. 2011 Sep 16;76(18):7438-48. doi: 10.1021/jo201209x. Epub 2011 Aug 24.
Catalytic intramolecular alkene aziridination of sulfamate is an emerging methodology for the asymmetric synthesis of chiral functionalized amines involving the formation of bicyclic aziridines. This study demonstrates the ability of the latter to undergo ring-opening with various carbon nucleophiles: Grignard reagents, lithium salts of terminal alkynes, dithiane, malonate. These S(N)2-type reactions occur with high levels of regio- and chemoselectivity to generally afford seven-membered cyclic sulfamidates in good yields. Carbon nucleophiles have also been found to react with these sulfamidates provided that the sulfamate ester has been previously activated by introduction of a tosyl substituent on the NH group. The versatility of this strategy has been illustrated with the syntheses of spisulosine and its fluoro analogue.
亚磺酰胺的催化分子内烯烃氮丙啶化是一种新兴的方法，用于涉及双环氮丙啶形成的手性官能化胺的不对称合成。本研究表明，后者能够与各种碳亲核试剂开环反应：格氏试剂、末端炔烃的锂盐、二硫杂环戊烷、丙二酸酯。这些 S(N)2 型反应具有高度的区域和化学选择性，通常以良好的收率得到七元环的环状磺酰胺酯。已经发现碳亲核试剂也可以与这些磺酰胺酯反应，只要磺酰胺酯的 NH 基团上已经通过引入对甲苯磺酰基而被激活。该策略的多功能性已通过 spisulosine 及其氟类似物的合成得到了说明。
