Phosphorodiamidites reactions with

Reactions with phosphorodiamidites Replacement of chlorine by alkyl... 

Phosphorodiamidites, e.g. (48), and M-chloroamines (49) gave exclusively di-amidochloridates, e.g. (50), in methylene chloride, whereas in petroleum ether some amidate, e.g. (51), was formed as well. The reactions of carbon tetrachloride with alkylbis(dialkylamino)phosphines (52) have been further studied this year. The remarkable rearrangement (53) to (54) occurs only with large isopropyl substituents on nitrogen, and with alkyl or hydrogen on the ylidic carbon. 

Certain P-chiral phosphorodiamidite ligands (e.g., 30A, 30B) complex with iridium(I) to form catalysts for promoting reaction of cinnamyl methyl carbonate with ArOH to form chiral aryl a-vinylbenzyl ethers. ... 

Sal keeva et al. studied the reactions of ethyl and /-butyl phosphorodiamidites with chloroacetone, bromoacetone, and a-chloroethyl acetate. The reaction pathway is determined by the structure of the intermediate quasiphosphonium compound responsible for the formation of the Arbuzov products as well as for the occurrence of the anomalous reaction yielding vinyl phosphate (Perkow product).26 The yield of the Arbuzov product increases from chloroacetone to bromoacetone, because the anions of low basicity are more rapidly ionized, which facilitates the formation of the ionic form of the intermediate. Also /-butyl phosphorodiamidite forms via Arbuzov reaction as the major product, because the second stage of the S l reaction is accelerated.26... 

Diphenylacetylenes. In a recent synthesis of diphenylacetylenes, the phos-phorochloridite (1) was allowed to react with a benzyl alcohol in the presence of triethylamine to form a phosphorodiamidite (2). Reaction of (2) with a benzo-trichloride gave (3), which was converted into a diphenylacetylene (4) on dehydrochlorination. Diphenylacetylene itself was obtained in 62% overall yield ... 

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