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Selective Synthesis of Cyclooctanoids by Radical Cyclization of Seven‐Membered Lactones: Neutron Diffraction Study of the Stereoselective Deuteration of a Chiral Organosamarium Intermediate
Author(s) -
JustBaringo Xavier,
Clark Jemma,
Gutmann Matthias J.,
Procter David J.
Publication year - 2016
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/anie.201606792
Subject(s) - stereoselectivity , radical cyclization , chemistry , samarium , quenching (fluorescence) , stereochemistry , organic chemistry , catalysis , physics , quantum mechanics , fluorescence
Seven‐membered lactones undergo selective SmI 2 –H 2 O‐promoted radical cyclization to form substituted cyclooctanols. The products arise from an exo‐mode of cyclization rather than the usual endo‐attack employed in the few radical syntheses of cyclooctanes. The process is terminated by the quenching of a chiral benzylic samarium. A labeling experiment and neutron diffraction study have been used for the first time to probe the configuration and highly diastereoselective deuteration of a chiral organosamarium intermediate.