投中国化学论文.docVIP

Palladacycle-catalyzed carbonylation of aryl iodides or bromides with aryl formates Guangwei Chen a, Yuting Leng a*, Fan Yang a, Shiwei Wang b， Yangjie Wu a* a The College of Chemistry and Molecular Engineering, Key Laboratory of Applied Chemistry of Henan Universities, Key laboratory of Chemical Biology and Organic Chemistry of He nan Province, Zhengzhou University, Zheng zhou ,He nan 450052, P. R. China; bCollege of Mechanics Engineering Science, Zhengzhou University, Zhengzhou, 450001 Henan, China. ( Corresponding author. Tel.: 0371 fax: +037167767993; e-mail: wyj@; yutingleng@ An efficient palladacycle-catalyzed aromatic carbonylation reaction of aryl formates with aryl iodides or bromides has been developed. Commercially available and easily prepared aryl formates were employed as carbonyl sources without the use of external carbon monoxide. The present catalytic system shows broad functional group tolerance and affords aryl benzoate derivatives in good to excellent yields. Keywords :carbonylation, aryl formates, palladacycle, catalysis Introduction Carbonylation reactions of aryl halides have become one of the most important transformations for the synthesis of various aromatic carboxylic acid derivatives, which existed in pharmaceuticals and agrochemicals.[1] The conventional strategy for the carbonylation conversion involved halogen metal exchange by alkyllithium or Grignard reagents and subsequent addition to carbon dioxide. Later, an efficient and complementary methodology was developed by employing a highly toxic gas of carbon monoxide as carbonyl source.[2] Therefore, exploring alternative methods avoiding the use of CO gas has received significant interest during recent years.[3] The first successful carbonylation of aryl bromides and chromium complexes of aryl chlorides with alkyl formates has been achieved by Carpentier and Mortreux et al.[4] Then, Jenner and Bentaleb proved carbonylations towards benzoic acid salts.[5] In 2010, Belle