Reactions of phosphonamidic acids and phosphonamidothioic acids with alcohols: mechanistic differences revealed by differing responses to steric effects

The formation of RP(X)(OH)OR' (R=Pr-i or Bu-t, R'=Me or Pr-i) from RP(X)(OH) NHBut and R'OH in CDCl3 is insensitive to steric effects when X=S but not when X=O (>10(3) times slower with R=Bu-t, R'=Pr-i than with R=Pr-i, R'=Me), pointing to a dissociative elimination-addit...

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Bibliographic Details
Published inChemical communications (Cambridge, England) no. 17; pp. 2200 - 2201
Main Authors Harger, MJP, Preston, C
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 01.01.2003
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
METAPHOSPHATE
PHOSPHORAMIDATE
TERT-BUTYLAMINE
PHOSPHORYLATION
SUBSTITUENTS
MONOESTERS
HYDROLYSIS
GENERATION
ETHYL METATHIOPHOSPHATE
AMIDES
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Summary:The formation of RP(X)(OH)OR' (R=Pr-i or Bu-t, R'=Me or Pr-i) from RP(X)(OH) NHBut and R'OH in CDCl3 is insensitive to steric effects when X=S but not when X=O (>10(3) times slower with R=Bu-t, R'=Pr-i than with R=Pr-i, R'=Me), pointing to a dissociative elimination-addition mechanism (metathiophosphonate intermediate) when X=S but an associative S(N)2(P) mechanism when X=O.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1359-7345
1364-548X
DOI:10.1039/b307206a