苯硒基的三重作用使得α-异氰基乙酸盐、苯乙烯基硒酮和水能够一锅法合成 1,3-噁唑烷-2-酮。

Triple role of phenylselenonyl group enabled a one-pot synthesis of 1,3-oxazinan-2-ones from α-isocyanoacetates, phenyl vinyl selenones, and water.

机构信息

Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne , EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne, Switzerland.

出版信息

J Am Chem Soc. 2014 Aug 13;136(32):11524-8. doi: 10.1021/ja506031h. Epub 2014 Aug 4.

DOI:10.1021/ja506031h

PMID:25066833

Abstract

Reaction of α-substituted α-isocyanoacetates with phenyl vinyl selenones in the presence of a catalytic amount of base (DBU or Et3N, 0.05-0.1 equiv) followed by addition of p-toluenesulfonic acid (PTSA, 0.1-0.2 equiv) afforded 4,4,5-trisubstituted 1,3-oxazinan-2-ones in good to excellent yields. Enantiomerically enriched heterocycles can also be prepared using a Cinchona alkaloid-derived bifunctional organocatalyst for the Michael addition step. The phenylselenonyl group served as an activator for the Michael addition, a leaving group and a latent oxidant in this integrated reaction sequence.

摘要

在催化量的碱（DBU 或 Et3N，0.05-0.1 当量）存在下，α-取代的α-异氰基乙酸酯与苯乙烯基硒酮反应，然后加入对甲苯磺酸（PTSA，0.1-0.2 当量），以良好至优异的收率得到 4,4,5-三取代的 1,3-恶唑烷-2-酮。使用金鸡纳生物碱衍生的双功能有机催化剂也可以制备对映体富集的杂环，用于迈克尔加成步骤。在这个综合反应序列中，苯基硒酮基既是迈克尔加成的活化剂，也是离去基团和潜在的氧化剂。