Heme-based catalysis for sustainable carbene transfer chemistry: computational mechanistic investigations

diazo and non-diazo precursors were revealed. Besides the basic mechanisms discovered for multiple heme carbene transfer reactions such as cyclopropanations and X-H insertions (X = Si, C, N) with many experimental features reproduced, details of how the carbene substituent, axial ligand, porphyrin substituent, and substrate substituent influence the reactivity were also examined to help future reaction design. In addition, the mechanistic origins of stereoselectivities and chemoselectivities for some important experimental heme carbene transfer reactions were disclosed to further advance this field. The interesting mechanistic results summarized in this review will facilitate the application of new-to-nature heme based biocatalysis.