Dishman, Sarah N. published the artcileDivergent stereochemical outcomes in the insertion of donor/donor carbenes into the C-H bonds of stereogenic centers, Computed Properties of 86-48-6, the publication is Chemical Science (2022), 13(4), 1030-1036, database is CAplus and MEDLINE.
Herein, the insertion of donor/donor carbenes into stereogenic carbon centers allowing access to trisubstituted benzodihydrofurans in a single step was reported. This study illuminates, for the first time, the stereochem. impact on the carbene center and delineates the structural factors that enable control over both stereogenic centers. Sterically bulky, highly activated C-H insertion centers exhibit high substrate control yielding a single diastereomer and a single enantiomer of product regardless of the catalyst used. Less bulky, less activated C-H insertion centers exhibit catalyst control over the diastereomeric ratio (dr), where a single enantiomer of each diastereomer was observed with high selectivity. A combination of exptl. studies and DFT calculations was used to elucidate the origin of these results. First, hydride transfer from the stereogenic insertion site proceeds with high stereoselectivity to the carbene center, thus determining the absolute configuration of the product. Second, the short lived zwitterionic intermediate can diastereoselectively ring-close by a hitherto unreported SE2 mechanism that was either controlled by the substrate or the catalyst. These results demonstrate that donor/donor carbenes undergo uniquely stereoselective reactions that originate from a stepwise reaction mechanism, in contrast to the analogous concerted reactions of carbenes with one or more electron-withdrawing groups attached.
Chemical Science published new progress about 86-48-6. 86-48-6 belongs to alcohols-buliding-blocks, auxiliary class Organic Pigment,Natural product, name is 1-Hydroxy-2-naphthoic acid, and the molecular formula is C11H8O3, Computed Properties of 86-48-6.
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