Carbene reactivity from alkyl and aryl aldehydes

L Zhang, BM DeMuynck, AN Paneque, JE Rutherford… - Science, 2022 - science.org
L Zhang, BM DeMuynck, AN Paneque, JE Rutherford, DA Nagib
Science, 2022science.org
Carbenes are highly enabling reactive intermediates that facilitate a diverse range of
otherwise inaccessible chemistry, including small-ring formation and insertion into strong σ
bonds. To access such valuable reactivity, reagents with high entropic or enthalpic driving
forces are often used, including explosive (diazo) or unstable (gem-dihalo) compounds.
Here, we report that common aldehydes are readily converted (via stable α-acyloxy halide
intermediates) to electronically diverse (donor or neutral) carbenes to facilitate> 10 reaction …
Carbenes are highly enabling reactive intermediates that facilitate a diverse range of otherwise inaccessible chemistry, including small-ring formation and insertion into strong σ bonds. To access such valuable reactivity, reagents with high entropic or enthalpic driving forces are often used, including explosive (diazo) or unstable (gem-dihalo) compounds. Here, we report that common aldehydes are readily converted (via stable α-acyloxy halide intermediates) to electronically diverse (donor or neutral) carbenes to facilitate >10 reaction classes. This strategy enables safe reactivity of nonstabilized carbenes from alkyl, aryl, and formyl aldehydes via zinc carbenoids. Earth-abundant metal salts [iron(II) chloride (FeCl2), cobalt(II) chloride (CoCl2), copper(I) chloride (CuCl)] are effective catalysts for these chemoselective carbene additions to σ and π bonds.
AAAS
以上显示的是最相近的搜索结果。 查看全部搜索结果