Throughout the methodology campaign that the Davies group has endeavored, the utility of donor/acceptor (D/A) carbene sources were highly focused on aryldiazoacetates. This current study expands the utility of these D/A carbenes to aryl diazoketones, which act as efficient D/A carbene sources to enact highly regio-, stereo- and diastereoselective C-H functionalization of activated secondary C-H bonds. The aryl diazoketone circumvents the thermally-mediated Wolff-rearrangement when the phthalimido dirhodium tetracarboxylate catalyst - Rh2(S-TPPTTL)4 is used. A reactivity map was developed to explore functional group tolerance in this new aryl diazoketone system. Furthermore, the new ketone handle opens up new chemical space for post-functionalization transformation, such as the Beckmann Rearrangement, to access chiral benzylamides, which represent an important class of building blocks for pharmaceutically relevant compounds. The utility of this transformation leverages the requirement of a low catalyst-loading and a relatively stable D/A carbene source to achieve highly stereo- and regioselective 2o C-H insertions.

Site-selective and enantionselective C-H functionalization with diazoketones

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ACS Fall 2022

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