2015
DOI: 10.1021/jacs.5b10299
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Remote Oxidation of Aliphatic C–H Bonds in Nitrogen-Containing Molecules

Abstract: Nitrogen heterocycles are ubiquitous in natural products and pharmaceuticals. Herein, we disclose a nitrogen complexation strategy that employs a strong Brønsted acid (HBF4) or an azaphilic Lewis acid (BF3) to enable remote, non-directed C(sp3)—H oxidations of tertiary (3°), secondary (2°), and primary (1°) amine- and pyridine- containing molecules with tunable iron catalysts. Imides resist oxidation and promote remote functionalization.

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Cited by 181 publications
(151 citation statements)
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References 29 publications
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“…13 More recently, we and others have leveraged this protonation strategy to achieve transition-metal catalyzed remote oxyfunctionalization of a more diverse variety of nitrogen-containing substrates, using K 2 PtCl 6 , 9 Fe(PDP), 14 and Mn/Ru-based catalysts. 15 However, all of these reactions exhibit limitations with respect to substrate scope and/or selectivity.…”
mentioning
confidence: 99%
“…13 More recently, we and others have leveraged this protonation strategy to achieve transition-metal catalyzed remote oxyfunctionalization of a more diverse variety of nitrogen-containing substrates, using K 2 PtCl 6 , 9 Fe(PDP), 14 and Mn/Ru-based catalysts. 15 However, all of these reactions exhibit limitations with respect to substrate scope and/or selectivity.…”
mentioning
confidence: 99%
“…( C ) Cycloheximine derivative (+)-260 is oxidized at C19–H, which is furthest away from the multiple EWGs of the molecule. 234 …”
Section: Figurementioning
confidence: 99%
“…Within the range of practically promising catalyst systems studied, the Mn-aminopyridine catalysts (1) are used in very small amount (0.1 mol %; structurally similar Fe complexes are typically used in up to 15 mol % loadings [29][30][31][32][33][34]); (2) require a small (1.3 equiv.) excess of the green oxidant-commercially available 30% aqueous H 2 O 2 ; and (3) exhibit reasonably high yields in the oxidation of differently p-substituted cumenes, ensuring high cumyl alcohol selectivity [86].…”
Section: Initially Costas and Co-workers Reported That Complexes [(Mmentioning
confidence: 99%
“…First examples of non-heme-Fe-catalyzed oxidations appeared in early 1990s [24,28]; however, the breakthrough was achieved after 2007, when White with co-workers contributed a series of milestone works, presenting the bipyrrolidine-derived non-heme iron catalyst 1 ( Figure 1) and its structural analogs, ensuring reasonably high level of predictability in the selective oxidation of C(sp 3 )-H groups [29][30][31][32][33][34]. In competitive contribution, Costas and co-workers showed that the introduction of additional steric crowd at the pyridine moieties, as well as manipulating with the symmetry of the chiral ligand can divert the oxidation selectivity from 3° C(sp 3 )-H bonds to stronger 2° C(sp 3 )-H bonds, which is critical for the selective oxygenation of complex molecules such as natural products [35][36][37][38].…”
Section: Introductionmentioning
confidence: 99%