Takeishi Kenzo, Sugishima Koudai, Sasaki Kaori, Tanaka Ken
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan.
Chemistry. 2004 Nov 5;10(22):5681-8. doi: 10.1002/chem.200400679.
A novel intramolecular hydroacylation of 5- and 6-alkynals leading to alpha-alkylidenecycloalkanones was accomplished by using cationic a rhodium(I)/BINAP complex. For all cyclizations described, a single (E)-olefin isomer was obtained. At elevated temperature, hydroacylation and double bond migration of 5- and 6-alkynals proceeded in a one-pot reaction to give cycloalkenones. An intramolecular hydroacylation of a 7-alkynal was unsuccessful. This method represents an attractive new route to highly functionalized alpha-alkylidenecycloalkanones and cycloalkenones.
通过使用阳离子铑（I）/联萘酚膦配体（BINAP）络合物，实现了一种新颖的5-和6-炔醛分子内氢酰化反应，生成α-亚烷基环烷酮。对于所描述的所有环化反应，均得到单一的（E）-烯烃异构体。在升高的温度下，5-和6-炔醛的氢酰化反应和双键迁移在一锅反应中进行，生成环烯酮。7-炔醛的分子内氢酰化反应未成功。该方法为制备高度官能化的α-亚烷基环烷酮和环烯酮提供了一条有吸引力的新途径。
