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Nucleophilic Reactivity of the Thiophosphoryl Group
Author(s) -
Teichmann H.,
Hilgetag G.
Publication year - 1967
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.196710131
Subject(s) - chemistry , nucleophile , sulfur , alkyl , reactivity (psychology) , isomerization , halogen , alkylation , carbon fibers , medicinal chemistry , base (topology) , organic chemistry , catalysis , medicine , mathematical analysis , alternative medicine , materials science , mathematics , pathology , composite number , composite material
The difference in the nucleophilic reactivities of the and groups can be satisfactorily explained on the basis of Pearson's acid‐base concept [21] . The thiophosphoryl sulfur is a typical “soft base”, and reacts preferentially with sub‐group B metals, halogens, and sp 3 hybridized carbon, whereas it is largely inert to “hard acids” such as protons, carbonyl carbon, and tetrahedral phosphorus. Since a nucleophilic attack by the thiophosphoryl sulfur leads to a decrease in the charge density of the phosphorus atom, the latter (or the α‐carbon atom in O‐alkyl esters) becomes more open to nucleophilic attack. This reaction principle forms the basis of sulfur exchange, dealkylation, isomerization, and the Pistschimuka and Michalski reactions.