Theoretical investigation on regioselectivity of aromatic ketones in the addition with olefin catalyzed by RuH_2(CO)(PPh_3)_3  

作　　者：雷鸣 冯文林 杜洪光 徐振峰 

机构地区：[1]Department of Applied Chemistry, Beijing University of Chemical Technology, Beijing 100029, China [2]Department of Chemistry, Beijing Normal University, Beijing 100875, China

出　　处：《Science China Chemistry》2000年第4期412-420,共9页中国科学（化学英文版）

摘　　要：Ab initio method is employed to study the structures of twelve aromatic ketones at HF/3-21G, HF/6-31G and HF/6-31G levels, respectively. A theoretical analysis is also carried out to study the regioselectivity and reactivity of aromatic ketones in the addition with olefin catalyzed by RuH2(CO)(PPh3)3. The results indicate that a U shape LUMO conjugation of aromatic ketones in a plane plays an important role in regioselectivity on the cleavage of p C-H bond and is a nec-essary factor to success of addition with olefin, and that sterle effect is an indispensable factor in forming additional ortho-product. Meanwhile, electronic effect may influence the rate of addition for the structures alike which only have different replacements in the same site of aromatic ring, such as furan, thiophene and pyrole. A possible catalytic reaction mechanism is proposed that the addition of C-H bond may be carried out by a coordination of aromatic ketones with Ru complex.Ab initio method is employed to study the structures of twelve aromatic ketones at HF/3-21G, HF/6-31G and HF/6-31G levels, respectively. A theoretical analysis is also carried out to study the regioselectivity and reactivity of aromatic ketones in the addition with olefin catalyzed by RuH2(CO)(PPh3)3. The results indicate that a U shape LUMO conjugation of aromatic ketones in a plane plays an important role in regioselectivity on the cleavage of p C-H bond and is a nec-essary factor to success of addition with olefin, and that sterle effect is an indispensable factor in forming additional ortho-product. Meanwhile, electronic effect may influence the rate of addition for the structures alike which only have different replacements in the same site of aromatic ring, such as furan, thiophene and pyrole. A possible catalytic reaction mechanism is proposed that the addition of C-H bond may be carried out by a coordination of aromatic ketones with Ru complex.

关 键 词：ab INITIO method ADDITION CLEAVAGE of C-H BOND Ru complex. 

分 类 号：O643.3[理学—物理化学]