Phospha-norbornadiene

Synthesis of [2,3-bis(methoxycarbonyl)-5,6-dimethyl-7-phenyl-7-phospha-norbornadiene](pentacarbonyl)tungsten (Structure 5 Scheme 1), the starting compound for the generation of (phenylphosphinidene)(pentacarbonyl)tungsten (Structure 6,... 

The transient electrophilic terminal phosphinidene 188, which is readily accessible by thermolysis of 7-phospha-norbornadiene complex 187 (Scheme 59), is a powerful precursor to phospholenes. For example, it reacts with ethoxyacetylene to give phosphole 189, which upon hydrolysis affords the 2-phospholene complex 190 (Scheme 59)... 

In aqueous two-phase hydroformylation of 1-octene and 1-dodecene the amphiphilic ligands of type 25 (n = 10, 12) have been shown to form Rh catalysts that are superior to Rh/TPPTS systems [129]. The bicyclic ligands 26 were considered to be of interest as substitutes for TPPMS in the new oxo process developed by Union Carbide for the hydroformylation of higher olefins using N-methylpyrroli-done or polyalkylene glycols as solvents [7, 51, 52], Rh(I) complexes [Rh(26)2]+ [96] showed, however, a very poor performance as catalysts in biphasic systems for hydrogenation and hydroformylations in contrast to non-functionalized 1-phospha-norbornadiene [98], This was explained by formation of P,P(0) chelates blocking... 

A review of recent developments in 1,3-dipolar cycloaddition of nitrones with sila-, thia-, phospha-, and halo-substituted alkenes has been reported. A DFT study of solvent effects on the intermolecular 3-l-2-cycloaddition reaction of norbornadiene with 3,4-dihydroisoquinoline A(-oxide at 398.15 K indicated that the reaction proceeds via a synchronous concerted mechanism. Chiral imidazolidinone salts, in the absence of water, promote the 1,3-dipolar cycloaddition reaction of alanine-derived ketonitrones... 

---