Ni()-catalyzed nucleophilic substitution for the synthesis of allenylselenide

• Published in: Chemical communications (Cambridge, England) Vol. 61; no. 6; pp. 1192 - 1195
• Main Authors: Zeng, Ling-Hong, Cui, Ranran, Huang, Zhuo, Zhang, Qing-Wei
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 14.01.2025; Royal Society of Chemistry
• Subjects: Catalysts; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; Substitution reactions; Zinc salts; CHEMISTRY; PALLADIUM; SELENIUM
• ISSN: 1359-7345; 1364-548X; 1364-548X
• DOI: 10.1039/d4cc05065g

A method for synthesizing allenylselenides has been developed using readily available propargyl carbonate and phenylselenol. The reaction is catalyzed by Ni( ii ) and proceeds via a migratory insertion and β-oxygen elimination mechanism. Due to the strong interaction between Se and Ni leading to catalyst deactivation, zinc salt was used to mitigate the deleterious effects of Se anions on the catalyst, thereby facilitating the successful synthesis of the target products. A Ni( ii )-catalyzed substitution reaction for the synthesis of aryl allenylselenide has been developed with over 30 examples. The enantioselective version has also been preliminarily shown with one example.