Planar Polycyclic Oxaphosphoranes Incorporating a Benzophosphole Unit
摘要:
A facile method to synthesize quaternized benzophospholes on gram scale was reported, and the products were isolated by simple filtration. During this research, a series of s5-oxaphosphoranes incorporating polycyclic aromatic hydrocarbons (PAHs) were obtained. The grafting of sigma(5)-phenolate groups on the phosphorus center enhances the coplanarity of the system.
[EN] TETRAMERISATION OF ETHYLENE<br/>[FR] TÉTRAMÉRISATION D'ÉTHYLÈNE
申请人:SASOL TECH PTY LTD
公开号:WO2014181250A1
公开(公告)日:2014-11-13
A process for the tetramerisation of ethylene includes contacting ethylene with a catalyst under ethylene oligomerisation conditions. The catalyst comprises a source of chromium, a ligating compound, and an activator. The ligating compound includes a phosphine that forms part of a cyclic structure.
Abstract We have developed novel Cr(III) catalysts supported by asymmetic N,N-diphospholylamine ligands bearing a phenoxaphosphine group. Upon activation with MMAO-3A, the Cr(III) catalysts supported by the PNP ligands are highly active for ethylene tri-/tetramerization with considerable selectivity. The ligand substitution and oligomerization conditions are found to be essential to achieve high activity
摘要我们开发了新型的Cr(III)催化剂,该催化剂由带有苯氧磷膦基团的不对称N,N-二磷酸基胺配体担载。经MMAO-3A活化后,由PNP配体负载的Cr(III)催化剂具有很高的选择性,对乙烯三/四聚反应具有很高的活性。发现配体取代和低聚条件对于实现高活性和可控制的选择性是必不可少的。具有不对称二膦酰胺配体的催化体系显示出比对称配体所支持的体系更高的活性。具有N-环己基的不对称二磷烷基胺配体在35℃下对有价值的1-己烯(28.7%)和1-辛烷值(54.5%)的最高选择性达到282.2 kg /(g Cr / h),总选择性高达83.2%。低于80°C。
Hydroformylation of Internal Olefins to Linear Aldehydes with Novel Rhodium Catalysts
作者:Lars A. van der Veen、Paul C. J. Kamer、Piet W. N. M. van Leeuwen
Unprecedented high activities and selectivities were observed in the hydroformylation of internal octenes to linear products using rhodium catalysts with rigid diphosphane ligands. Dibenzophosphole 1 and a phenoxaphosphane analogue with bite angles of 120 and 119°, respectively, are suited for this.
SPANphos Ligands in Palladium-Catalyzed Asymmetric Fluorination
作者:Olivier Jacquet、Nicolas D. Clément、Carolina Blanco、Marta Martinez Belmonte、Jordi Benet-Buchholz、Piet W. N. M. van Leeuwen
DOI:10.1002/ejoc.201200223
日期:2012.9
The synthesis of new enantiopure wide-bite-angle diphosphanes is described as well as their use in the palladium-catalyzedasymmetricfluorination of α-cyanoacetates. Enantiomeric excesses up to 93 % were obtained when Pd(OAc) 2 -SPANphos was used as catalyst for the fluorination of ethyl 2-cyano-2-phenylacetate with N-fluorobenzenesulfonimide (NFSI).