Polystyryl diphenylphosphine

Table 1.6.8. Reagents derived from polystyryl diphenylphosphine Table 1.6.9. Chiral polymer-bound catalysts Table 1.6.10. Miscellaneous reagents...

Table 1.6.8. Reagents derived from polystyryl diphenylphosphine...

Me Me X-Br JO From polystyryl diphenylphosphine and P-cyclogeranyl bromide of P-geraniol (cf. Scheme /.6.27)24S Synthesis of cthylretinoate (48) from aldehyde 49 (Scheme 1.6.27)- ... 

R = H. Ph From polystyryl diphenylphosphine cross linked with 2, S and 20% DVB. - Comparison of olefin formation from aldehydes and ketones using polymeric phosphonium halides with different degree of crosslinking. 

X = Cl. Br. T Treatment of polystyryl diphenylphosphine with CL, Br, or I, in CH,CL.24 Halohydrins from epoxides yields and selectivities compare well with those obtained with monomeric triphenyl phosphine-halogen complexes.2 11 Open and cyclic acetals and thioacetals by treatment of aldehydes and ketones with alcohols or thiols in the presence of polystyryl diphenylphosphine iodine complex.249... 

In the area of 5 -di- and tri-phosphates, ATP, GTP, UTP and CTP, with deuterium in all of the 3 -, 4 -, and 5 -positions, have been made enzymically from the labelled ribose (Chapter 2) whilst chemical routes to the 5 -triphosphates of 4-thiouridine, 2-thiocytidine, 5-bromocytidine and [6- N]-adenosine have been described. Azidonucleosides can be converted by treatment with a polystyryl diphenylphosphine into polymer-bound phosphine imines (Vol. 28, p. 272) it has now been reported that the nucleoside phosphine imine can be converted to its 5 -triphosphate before hydrolysis to give the amine. The method was used to convert AZT into the 5 -triphosphate of 3 -amino-3 -deoxythymidine, amongst other cases.A method previously used to make the P -methyl-... 

Dithioacetals, 1,3-dithianes or 13-dithiolanes are prepared by reaction of the corresponding carbonyl compound in the presence of an acid catalyst (cone. HQ, Lewis acids such as Znh, BFs EtaO, TMS-Cl, etc.) with a thiol or dithiol. Silica gel treated with thionyl chloride was found to be an effective as well as selective catalyst for thioacetalization of aldehydes. Thioacetalization can also be achieved using a (polystyryl)diphenylphosphine-4odine complex as a catalyst Conversion of aldehydes or acetals into 1,3-dithianes is achieved with the aid of organotin thioalkoxides and organotin triflates or with 2,2-di-methyl-2-sila-l,3-dithiane. Direct conversion of carboxylic acids to 1,3-dithianes can be carried out by reaction with 1,3,2-dithiabomenane-dimethyl sulfide and tin(II) chloride or 1,3,2-dithiaborolene with trichloromethyllithium followed by basic hydrolysis. 

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