The catalytic transformation of a C(sp3)–H bond to a C(sp3)–C bond via an iron carbene intermediate represents a long-standing challenge. Despite the success of enzymatic and small molecule iron catalysts mediating challenging C(sp3)–H oxidations and aminations via high-valent iron oxos and nitrenes, C(sp3)–H alkylations via isoelectronic iron carbene intermediates have thus far been unsuccessful. Iron carbenes have been inert, or shown to favor olefin cyclopropanation and heteroatom-hydrogen insertion. Herein we report an iron phthalocyanine-catalyzed alkylation of allylic and benzylic C(sp3)–H bonds. Mechanistic investigations support that an electrophilic iron carbene mediates homolytic C–H cleavage and rebounds from the resulting organoiron intermediate to form the C–C bond; both steps are tunable via catalyst modifications. These studies suggest that for iron carbenes, distinct from other late metal carbenes, C–H cleavage is partially rate-determining and must be promoted to effect reactivity.

Allylic amination enables late-stage functionalization of natural products where allylic C−H bonds are abundant and introduction of nitrogen may alter biological profiles. Despite advances, intermolecular allylic amination remains a challenging problem due to reactivity and selectivity issues that often mandate excess substrate, furnish product mixtures, and render important classes of olefins (for example, functionalized cyclic) not viable substrates. Here we report that a sustainable manganese perchlorophthalocyanine catalyst, [Mn III (ClPc)], achieves selective, preparative intermolecular allylic C−H amination of 32 cyclic and linear compounds, including ones housing basic amines and competing sites for allylic, ethereal, and benzylic amination. Mechanistic studies support that the high selectivity of [Mn III (ClPc)] may be attributed to its electrophilic, bulky nature and stepwise amination mechanism. Late-stage amination is demonstrated on five distinct classes of natural products, generally with >20:1 site-, regio-, and diastereoselectivity.

Herein, we report the development of a photoredox-initiated frontal ring-opening metathesis polymerization (FROMP) chemical system. We found that a ruthenium-based, bis-N-heterocyclic carbene metathesis precatalyst was activated with 9-mesityl-10-phenylacridindium tetrafluoroborate, copper­(II) triflate, and a 455 nm light source. This chemistry was used to initiate the FROMP of dicyclopentadiene; once initiated, the heat released from the polymerization sustained a well-controlled reaction front. Variation in copper or metathesis precatalyst loading yielded front speeds ranging from 0.15 to 0.43 mm s–1 and front temperatures ranging from 140 to 205 °C. While the glass transition temperatures of the resultant polymers are lower than those derived with Grubbs’ second-generation catalyst, this chemical system provides extended pot life.

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