Kondoh Azusa, Aoki Takuma, Terada Masahiro
Department of Chemistry and ‡Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University , Aoba-ku, Sendai 980-8578, Japan.
Org Lett. 2014 Jul 3;16(13):3528-31. doi: 10.1021/ol501479t. Epub 2014 Jun 23.
A novel catalytic cyclization reaction of alkynyl α-ketoanilide was developed by utilizing the [1,2]-phospha-Brook rearrangement. This reaction involves the generation of an amide enolate via the umpolung process, that is the addition of dialkyl phosphite to a keto moiety followed by the [1,2]-phospha-Brook rearrangement, and the subsequent intramolecular addition of the enolate to an alkyne to afford 3,4-dihydro-2-quinolone derivatives. Under high-temperature reaction conditions, further rearrangement of the allylic phosphate moiety occurs to provide 2-quinolone derivatives.
通过利用[1,2]-磷杂-Brook重排反应，开发了一种新型的炔基α-酮酰胺催化环化反应。该反应涉及通过极性翻转过程生成酰胺烯醇盐，即亚磷酸二烷基酯加成到酮部分，随后进行[1,2]-磷杂-Brook重排，以及烯醇盐随后分子内加成到炔烃上，得到3,4-二氢-2-喹诺酮衍生物。在高温反应条件下，烯丙基磷酸酯部分会进一步重排，生成2-喹诺酮衍生物。
