%0 Journal Article
%A Martín, Angeles
%A Pérez-Martín, Inés
%A Quintanal, Luis M.
%A Suárez, Ernesto
%D 2007
%T Intramolecular 1,8- versus 1,6-Hydrogen
Atom Transfer between Pyranose Units
in a (1→4)-Disaccharide Model
Promoted by Alkoxyl Radicals.
Conformational and Stereochemical
Requirements
%U https://acs.figshare.com/articles/journal_contribution/Intramolecular_1_8_versus_1_6_Hydrogen_Atom_Transfer_between_Pyranose_Units_in_a_1_4_Disaccharide_Model_Promoted_by_Alkoxyl_Radicals_Conformational_and_Stereochemical_Requirements/3011185
%R 10.1021/ol070496q.s002
%2 https://acs.figshare.com/ndownloader/files/4712497
%K skeleton
%K Transfer
%K interglycosidic spiro ortho ester
%K abstraction
%K factor
%K intramolecular hydrogen atom transfer
%K derivative
%K Conformational
%K Pyranose Units
%K Disaccharide
%K Alkoxyl Radicals
%K formation
%K conformation
%K disaccharide
%K Stereochemical RequirementsThe stereochemical
%K Promoted
%K Model
%K pyranose units
%K transition
%K Intramolecular
%K trioxocane
%X The stereochemical and conformational factors controlling the intramolecular hydrogen atom transfer (HAT) reaction between the two pyranose
units in a (1→4)-disaccharide when promoted by a primary 6-O-yl radical are studied. Models with α-d-Glcp-(1→4)-β-d-Glcp or α-l-Rhamp-(1→4)-α-d-Galp skeletons lead exclusively to the abstraction of H−C-5‘ and the formation, through a nine-membered transition state, of a
1,3,5-trioxocane ring system in a stable boat-chair conformation. Notwithstanding, derivatives of α-l-Rhamp-(1→4)-α-d-Glcp abstract exclusively
H−C-1‘ through a seven-membered transition state and therefore lead to an interglycosidic spiro ortho ester.
%I ACS Publications