Iron-Catalyzed Carbenoid Insertion into C(sp3)–H Bonds

Abstract

An iron-catalyzed carbenoid insertion into C–H bonds of alkanes was developed with high activity (turnover numbers up to 690 in a gram-scale experiment) and chemoselectivity. This non-heme iron-catalyzed C(sp3)–H insertion reaction provides an efficient strategy for C–H functionalization.

Catalytic alkane C–H functionalization by carbene insertion into unactivated C(sp3)–H bonds

“…Subsequently, several catalysts, such as NCPS-Ru (Scheme 10, entry 2), 68 Cat. 14 (Scheme 10, entry 3), 69 Fe(ClO 4 ) 2 •xH 2 O + BPMEN (Scheme 10, entry 4) 70 and Tp (CF 3 ) 2 Ag(THF) (Scheme 10, entry 5), 71 Tp (CF3)2,Br Ag(THF) and Cat. 15, to enhance the site selectivity of the reaction (Scheme 10, entries 6 and 7).…”

“…13 (Scheme 9, entry 2), 67 NCPS-Ru (Scheme 9, entry 3), 68 Cat. 14 (Scheme 9, entry 4), 69 Fe(ClO 4 ) 2 · x H 2 O + BPMEN (Scheme 9, entry 5), 70 and Tp (CF 3 ) 2 Ag(THF) (Scheme 9, entry 6). 71 The introduction of a donor group could temper its electrophilicity and suppress the carbene dimerization process, thus allowing for exquisite site-selectivity.…”

“…Subsequently, several catalysts, such as NCPS-Ru (Scheme 10, entry 2), 68 Cat. 14 (Scheme 10, entry 3), 69 Fe(ClO 4 ) 2 · x H 2 O + BPMEN (Scheme 10, entry 4) 70 and Tp (CF 3 ) 2 Ag(THF) (Scheme 10, entry 5), 71 have been employed to catalyze the C–H bond insertion reactions of linear alkanes with 32a and 32b , resulting in high secondary C–H site selectivity. Recently, Pérez and coworkers employed two silver catalysts, Tp (CF 3 ) 2 ,Br Ag(THF) and Cat.…”

Recent advances in TBHP‐promoted heterocyclic ring construction via annulation/cyclization

“…An important class of heterocycles included in many licenced medications and therapeutic prospects are pyrazolo [3,4-b]pyridines [52]. After intramolecular cyclization and dehydroaromatization in the presence of Cu(OTf) 2 /TBHP, the reaction of 5-aminopyrazoles (49) with 1,3-diarylpropenes (50), mediated by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, produced a series of pyrazolo [3,4-b]pyridines (51) in moderate to excellent yields [53]. The reaction offers the benefits of a one-pot process, a broad substrate range, and great atom economy.…”

“…Scheme 33 illustrates the extent of research done on substituting D-glucose with mono-, di-, and poly-saccharides (53). L-arabinose, maltose, cellobiose, sucrose, and starch underwent a smooth conversion process in the reaction to generate compound 54 in yields ranging from 73% to 78%.…”