Selective Synthesis of Cyclooctanoids by Radical Cyclization of Seven-Membered Lactones: Neutron Diffraction Study of the Stereoselective Deuteration of a Chiral Organosamarium Intermediate
Seven-membered lactones undergo selective SmI2–H2O-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.
Just-Baringo, Xavier,Clark, Jemma,Gutmann, Matthias J.,Procter, David J.
supporting information
p. 12499 - 12502
(2016/10/13)
The First Tandem [2 + 2] Cycloaddition-Michael Reaction Using Ynolates: Facile Construction of Substituted Carbocycles
(matrix presented) A tandem [2 + 2] cycloaddition-Michael reaction using ynolate anions followed by decarboxylation produced polysubstituted five-, six-, and seven-membered cycloalkenes.