400-54-4Relevant articles and documents
A Sequential Route to Cyclopentenes from 1,6-Enynes and Diazo Ketones through Gold and Rhodium Catalysis
Kale, Balaji S.,Lee, Hsin-Fu,Liu, Rai-Shung
supporting information, p. 402 - 409 (2017/02/10)
This work reports the construction of cyclopentene cores from 1,6-enynes and aryl diazo ketones through two new reaction sequences involving initial gold-catalyzed cyclization of 1,6-enynes with diazo species, followed by rhodium-catalyzed skeletal rearrangement of the resulting 3-cyclopropyl-2-en-1-ones. In most instances the rhodium-catalyzed reactions afforded cyclopentene derivatives whereas several n-alkyl- or ortho-substituted phenyl ketones delivered seven-membered oxacycles. A plausible mechanism provides rationales for these two distinct products. (Figure presented.).
Synthesis and characterization of the titanium complexes bearing two regioisomeric trifluoromethyl-containing enaminoketonato ligands and their behavior in ethylene polymerization
Ye, Wei-Ping,Mu, Hong-Liang,Shi, Xin-Cui,Cheng, Yan-Xiang,Li, Yue-Sheng
experimental part, p. 9452 - 9465 (2010/03/04)
A series of new titanium complexes bearing two regioisomeric trifluoromethyl-containing enaminoketonato ligands (3a-h and 6a-h), [PhNCRCHC(CF3)O]2TiCl2 (3a, R = Me; 3b, R = n-C5H11; 3c, R = i-Pr; 3d, R = Cy; 3e, R = t-Bu; 3f, R = CHCHPh; 3g, R = Et; 3h, R = n-C11H23) and [PhNC(CF 3)CHC(R)O]2TiCl2 (6a, R = Ph; 6b, R = n-C 5H11; 6c, R = i-Pr; 6d, R = Cy; 6e, R = t-Bu; 6f, R = CHCHPh; 6g, R = CHPh2; 6h, R = CF3) have been synthesized and characterized. X-ray crystal structures analyses suggest that complexes 3c-e and 6c-d all adopt a distorted octahedral geometry around the titanium center. Complexes 3c, 3d and 6c display a cis-configuration of the two chlorine atoms around the titanium center, while complex 6d shows a trans-configuration of the two chlorine atoms. Especially, the configurational isomers (cis and trans) of complex 3e were identified both in solution and in the solid state by NMR and X-ray analyses. With modified methylaluminoxane as a cocatalyst, all the complexes are active towards ethylene polymerization, and produce high molecular weight polymers. With the variation of the relative position of the imino group and the trifluoromethyl group of the β-enaminoketonato ligands, the polymerization behavior of the catalysts changed remarkably. It is observed that the substituent directly joined to the carbonyl in the ligands plays an important role for both the catalytic activities and the properties of the polymers produced. The Royal Society of Chemistry 2009.
