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Reexamination of the Evidence for Solvent‐Induced Intramolecular Electrophilic Catalysis by a cis Vicinal Hydroxyl Group in Ribonucleoside Phosphorylation Reactions
Author(s) -
Cullis Paul M.,
Harger Martin J. P.,
Lee Michael
Publication year - 2000
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/1521-3773(20001201)39:23<4245::aid-anie4245>3.0.co;2-k
Subject(s) - vicinal , chemistry , intramolecular force , electrophile , diastereomer , ribonucleoside , hydrogen bond , stereochemistry , catalysis , organic chemistry , molecule , rna , biochemistry , gene
The vicinal hydroxyl group accelerates the second stage of the sequence leading to 2′‐ and 3′‐dialkyl nucleotide triesters 3 and 4 because it enables formation of the reactive 2′,3′‐cyclic phosphorochloridate intermediate 2 a/b (mixture of diastereoisomers); it is not because of electrophilic catalysis (hydrogen bonding) in acyclic phosphorodichloridates as recently proposed.