
Journal of Molecular Catalysis A: Chemical p. 127 - 133 (2002)
Update date:2022-07-29
Topics:
Tagliatesta, Pietro
Pastorini, Alessandra
The rhodium meso-tetraphenylporphyrins catalysed cyclopropanation reactions of styrene, cyclohexene and norbornene by ethyldiazoacetate (EDA), have been investigated. The electronic effects of the bromine groups in the β-positions of the porphyrins can be correlated to the syn/anti ratio obtained for the reaction products in the case of styrene, showing a good linear correlation between the sum of the Hammett's σp and the logarithm of the obtained selectivity. A decrease in the stereochemical ratio on increasing the number of halogen atoms was observed. This is not the case for cyclohexene and norbornene which show a different behavior and do not give good linear correlation. Furthermore, when the rhodium porphyrins have bulky methoxy substituents in the ortho-positions of the phenyl rings, comparing with the simple rhodium meso-tetraphenylporphyrin, the isomeric ratios decrease dramatically for styrene whilst for the other substrates remain almost in the same range. On the contrary, using a rhodium porphyrin bearing chlorine groups in the ortho-positions of the phenyl rings, the ratios increase, reaching higher values. These observations suggest the presence of different factors involved in determining the isomeric ratios. The electron-withdrawing effects of the substituents in the β-positions seem to influence the stereoselectivity giving the less hindered isomer while the chlorine bulky substituents in the ortho-phenyl positions can compensate this trend.
Beijing Mashi Fine Chemical Co.,Ltd.
Contact:+86-10-61271592
Address:Room 506, Section B, Kaichi Mansion, Industrial Development
Reliability Assessment Solutions (Changhzou) Co., Ltd.
Contact:86-519-85607515
Address:RM 601-603 BD1 Fuchen Mansion, 8 Taihu East RD, Xinbei District, Changhou, Jiangsu 213022, China
shanghai hekang chemical co.ltd
Contact:021-54173790
Address:328 WuHe Road, Building #A, 2nd Floor, Minhang, Shanghai 201109, China
Arshine Pharmaceutical Co., Limited
website:http://www.cnarshine.com
Contact:0731-88503671
Address:Room 1109.Block C3, Lugu Enterprise Plaza,No.27 Wenxuan Road,Changsha National Hi-Tech Industrial Development Zone,Hunan ,P.R.China
Ningbo Hi-tech Zone Nice-Synth Chemical Industry Ltd.
Contact:+86-(574)-81110986
Address:No. 1210, Building 3, Wante Business Centre, Hi-tech Zone, Ningbo
Doi:10.1248/cpb.50.372
(2002)Doi:10.1007/BF01518472
(1933)Doi:10.1021/ol0478638
(2004)Doi:10.1271/bbb.66.1671
(2002)Doi:10.1016/j.bmc.2007.11.074
(2008)Doi:10.1002/anie.201306688
(2013)