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Unexpected Loss of Stereoselectivity in Ring‐Opening Reaction of 2‐Alkoxy‐2‐Thio‐1,3,2‐Oxathiaphospholanes With a Pyrophosphate Anion
Author(s) -
Guga Piotr,
Tomaszewska Agnieszka
Publication year - 2015
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22398
Subject(s) - chemistry , stereoselectivity , thio , intramolecular force , stereochemistry , ligand (biochemistry) , chirality (physics) , ring (chemistry) , pyrophosphate , alkoxy group , nucleoside , ion , monomer , medicinal chemistry , catalysis , organic chemistry , chiral symmetry , biochemistry , receptor , physics , alkyl , quantum mechanics , quark , polymer , enzyme , nambu–jona lasinio model
A reaction of DBU promoted ring opening in nucleoside‐3'‐ O ‐ and nucleoside‐5'‐ O ‐(2‐thio‐4,4‐pentamethylene‐1,3,2‐oxathiaphospholane) monomers with a pyrophosphate or a methylenediphosphonate anion proceeds with substantial loss of stereoselectivity. Depending on the absolute configuration of the phosphorus atom, so far widely accepted the stereoretentive mechanism of condensation is accompanied by a stereoinvertive one, most likely employing an intramolecular ligand–ligand exchange in an uncharged intermediate . Chirality 27:155–122, 2015 . © 2014 Wiley Periodicals, Inc