Amido-groups as removable directing groups in palladium complex catalyzed carbon-hydrogen bond functionalization of benzoquinone derivatives

• Main Authors: Jia-Nan Jhou, 周家男
• Other Authors: 洪豐裕
• Format: Others
• Language: zh-TW
• Published: 2018
• Online Access: http://ndltd.ncl.edu.tw/handle/a56zvt

碩士 === 國立中興大學 === 化學系所 === 106 === In this study, N-(3,6-dioxocyclohexa-1,4-dien-1-yl)acetamide 2a-BQ and triethylamine were used as the starting materials and Pd(II) species were used as the catalyst precursors in one-pot reaction to functionalize the carbon-hydrogen bonds on the both sides of benzoquinone to form 1H-benzo[f]indole-4,9-dione 3a and an amination product 4a. The structure of 4a was determined by single crystal X-ray diffraction methods and it was confirmed that the amination reaction occurred in the para-position of the acetamyl group of 2a-BQ. Tripropylamine and tributylamine, which have higher carbon number than triethylamine, were used as starting materials to carry out the reaction under the same condition. In addition to the production of benzene-containing indolequinone derivative, 3c, the amination products 4b-4c in the para-position were observed as well. It also found that an indolequinone derivatives, 3d-3e, having substitution on the newly-generated benzene ring were obtained. Also, the structure of 4c was determined by single crystal X-ray diffraction methods. Based on the productions of various indolequinone derivatives and amination products, we assumed that the transition metal complex Pd(OAc)2 or PdCl2 firstly catalyzed amine and followed by attacking 2a-BQ to the formation of a cyclization product. A mechanism was proposed to account for the experimental observations.