Phosphorus compounds, catalysis

Many catalysts, both immobilized (on solid state supports) and heterogeneous, contain phosphines and other phosphorus compounds, so that solid state NMR has become an invaluable tool in the study of catalysis. 

Partitioning of carbocations between addition of nucleophiles and deprotonation, 35, 67 Perchloro-organic chemistry structure, spectroscopy and reaction pathways, 25, 267 Permutational isomerization of pentavalent phosphorus compounds, 9, 25 Phase-transfer catalysis by quaternary ammonium salts, 15, 267 Phosphate esters, mechanism and catalysis of nucleophilic substitution in, 25, 99 Phosphorus compounds, pentavalent, turnstile rearrangement and pseudoration in permutational isomerization, 9, 25... 

The author hopes that this chapter has convinced the readers of the value of homogeneous catalysis for the synthesis of organophosphorus compounds and for organo-heteroatom compounds in a broader sense. Hydrosilylation and hydroboration are indispensable modern synthetic reactions in this category. The H-P addition reactions herein described joins them as a third member. Although this chapter does not cover, the addition reactions of the S-P and Se-P bonds in thiophosphates [39] and selenophosphates [40] to alkynes also proceed in the presence of transition metal catalysts. In view of the wide use of phosphorus compounds, the new procedures will find practical applications. 

H. B. Kagan, Chiral Ligands for Asymmetric Catalysis, in J. D. Morrison, ed., Asymmetric Synthesis, Vol. 5, Chap. 1, Academic Press, New York, 1985 H. B. Kagan and M. Sasaki, Optically Active Phosphines Preparation, Uses and Chiroptical Properties, in F. R. Hartley, ed., The Chemistry of Organo-phosphorus Compounds, Vol. 1, Chap. 3, John Wiley Sons, New York, 1990. 

Hydroformylation - [CARBON MONOXIDE] (Vol 5) - [OXO PROCESS] (Vol 17) -of allyl alcohol [ALLYL ALCOHOL AND MONOALLYL DERIVATIVES] (Vol 2) -catalysts for [CATALYSIS] (Vol 5) -C-19 dicarboxylic acids from [DICARBOXYLIC ACIDS] (Vol 8) -of ethylene [ETHYLENE] (Vol 9) -of ethylene [PROPYL ALCOHOLS - N-PROPYLALCOLHOL] (Vol 20) -of maleate and fumarate esters [MALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -phosphine catalyst [PHOSPHORUS COMPOUNDS] (Vol 18) -platinum-group metal catalysts for [PLATINUM-GROUP METALS] (Vol 19) -rhodium catalysis [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -ruthenium cmpds or catalyst [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -use of coordination compounds [COORDINATION COMPOUNDS] (Vol 7)... 

The effect of phosphorus on PD depends on the catalyst preparation method. The PD of catalysts prepared by impregnation decreases with phosphorus loading, whereas that of catalysis derived from the hydrogel or sol-gel methods tends to increase in some cases. Introduction of phosphorus compounds in the sol-gel procedure may affect the hydrolysis and condensa-... 

Due to the great importance of phosphines and phosphinites as chiral ligands for asymmetric catalysis, several hundred compounds of this type have been prepared. In this section, only those compounds which have been mentioned in this Houben-Weyl volume will be discussed. Because of their close relation to the specific topics, biaryl phosphines have already been mentioned in Section 6 and ferrocene derivatives in Section 7.1. All other phosphorus compounds are treated here. An excellent review on the synthesis of enantiomerically enriched compounds where phosphorus is a stereogenic center has recently been published73. 

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