One‐pot Synthesis of Alkynylated Coumarins via Rhodium‐Catalyzed Annulation of Aryl Thiocarbamates with 1,3‐Diynes or Terminal Alkynes

• Published in: Advanced synthesis & catalysis Vol. 360; no. 7; pp. 1328 - 1333
• Main Authors: Gao, Yuan, Zeng, Fenfen, Sun, Xudong, Zeng, Minfeng, Yang, Zhen, Huang, Xianqiang, Shen, Guodong, Tan, Yongsheng, Feng, Ruokun, Qi, Chenze
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 03.04.2018; Wiley Subscription Services, Inc
• Subjects: 1,3-Diynes; Alkanes; Alkenes; Alkynes; Alkynylated coumarin; Aromatic compounds; Chemical reactions; Chemical synthesis; Chemistry; Chemistry, Applied; Chemistry, Organic; C−H/C−N bond cleavage; Dichloromethane; Fluorescence; Fluorescence properties; Hydrogen bonds; Organic chemistry; Physical Sciences; Rhodium; Rhodium-catalyzed; Science & Technology; Terminal alkynes; PALLADIUM; Terminal alkynes; H ACTIVATION/1,3-DIYNE STRATEGY; Alkynylated coumarin; CLEAVAGE; 1; Fluorescence properties; C-N bond cleavage; FLUORESCENT DYES; CROSS-BENZANNULATION; DEVICES; BENZANNULATION REACTION; ENERGY-TRANSFER; 3-Diynes; CONJUGATED ENYNES; Rhodium-catalyzed; C-H; DIYNES
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201701388

A convenient and selective synthesis of alkynylated coumarins from various aryl thiocarbamates and 1,3‐diynes or terminal alkynes via rhodium‐catalyzed C−H bond activation has been developed. In this transformation, both symmetrical and asymmetrical 1,3‐diynes could be applicable, obtaining various 3‐alkynylated coumarins in moderate to excellent yields. When the substituent is aryl group, the resulting compounds were found to exhibit intense fluorescence in the range of 412–443 nm with quantum yield of up to 0.57 in CH2Cl2. Moreover, the internal alkynes were readily converted to 1,2‐dione, olefins, alkanes, and bisheterocycles under certain conditions.