由市售或合成的氨基醇制备一系列对映体纯的2- [2-(二芳基膦基)芳基]-恶唑啉。对于恶唑啉的形成,采用了三种程序:(i)与2-卤代苯甲酸一锅缩合,(ii)ZnCl 2与2-卤代苯甲腈-苯胺催化缩合,和(iii)通过2-卤代苯甲酰胺的三步顺序和甲苯磺酸盐或氯化物。通过非对映选择性亲核取代Ar 1 Ar 2 PC1的卤化物或通过LiPAr 1 Ar 2亲核芳族取代制备含有立体异构磷的膦恶唑啉。另外,制备了硫和硒类似物。
P-Stereogenic Phosphorus Compounds: Effect of Aryl Substituents on the Oxidation of Arylmethylphenylphosphanes under Asymmetric Appel Conditions
作者:Kamalraj V. Rajendran、Lorna Kennedy、Declan G. Gilheany
DOI:10.1002/ejoc.201000733
日期:2010.10
The effects of aryl ringsubstitution on the dynamic resolution of aryl(methyl)phenylphosphanes under asymmetric Appel reaction conditions have been studied. As expected, substitution at the ortho position strongly affects the degree ofstereoselection that can be achieved. Unexpectedly, however, there was no variation of stereoselectivity with the electronic nature of the para substituents, which suggests
The iodocarbocyclization of the tethered alkyne is an important method for diverse family of cyclic molecules. Using the phosphoryl group as a new linker leads to the formation of α‐iodo‐substituted spiro‐conjugated phosphinolines and phosphepines, which were further transformed to π‐elongated derivatives and provided a phosphepine‐based AIE luminogen.
Mechanistic considerations made a decisive contribution to the development of new chiral P,N ligands L* containing tricarbonylcyclopentadienylmanganese (cymantrene). These ligands induce very high enantioselectivities (>99:1) in allylic substitutions of cyclic substrates 1 with formation of 2 (2-Bp=2-biphenylyl).