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 rea...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.展开更多
基金supported by National Key Basic Research Development Program of China(973)(2013CB733505,2013CB733501)National Natural Science Foundation of China(91334202)+2 种基金Natural Science Foundation of Jiangsu Province(BK2012421)Research Fund for the Doctoral Program of Higher Education of China(20123221120015)Project for Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)~~
文摘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.
