Manganese-Catalyzed C(sp2)–H Addition to Polar Unsaturated Bonds

Abstract

Transition-metal-catalyzed nucleophilic C-H addition of hydrocarbons to polar unsaturated bonds could intrinsically avoid pre-functionalization of substrates and formation of waste byproducts, thus featuring high step- and atom-economy. As the third most abundant transition metals, manganese-catalyzed C-H addition to polar unsaturated bonds remains challenging partially due to the difficulty in building a closed catalytic cycle of manganese. In the past few years, we have developed manganese catalysis to enable the sp2-hydrid C-H addition to polar unsaturated bonds (e.g. imines, aldehydes, nitriles), which will be mainly discussed in this personal account.

Regioselective ortho C–H insertion of N-nitrosoanilines with naphthoquinone carbenes

“…7 In recent years, their utility has been extended to transition metal-catalyzed migratory insertion reactions. 8 The ready aromatization of the quinone intermediates allowed the introduction of phenolic groups. In this paper, we would like to report a Rh( iii )-catalyzed migratory insertion of naphthoquinone carbenes into ortho C(sp 2 )–H bonds of N -nitrosoanilines.…”

Multiply exo‐Methylated Corannulenes

“…[23][24][25][26][27][28][29] We have been interested in developing new transformations by exploring reductive metalation of unsaturated bonds as a powerful method. [30][31][32][33][34][35] Recently, we reported a sodiumpromoted reductive boration of planar PAHs using trialkoxyborane as an electrophile. [33] This reductive transformation was then used for multiple alkylations of spherical C 60 fullerene using dialkyl sulfate.…”

Rhodium‐Catalyzed Asymmetric Arylation of Cyclobutenone Ketals

“…ring expansion or contraction) but the enantioselective functionalization of pre-existing cyclobutanes or cyclobutenes has recently emerged as a complementary approach. [3,[5][6][7] Tortosa and co-workers described a copper-catalyzed desymmetrization for the enantioselective synthesis of cyclobutylboronates. This approach yields 1,2,3-trisubstituted cyclobutanes that can readily undergo further modifications.…”