Comparative Study of the Catalytic Amination of Benzylic C–H Bonds Promoted by Ru(TPP)(py)₂ and Ru(TPP)(CO)

Abstract

The syntheses and structures of two new ZnII complexes, a 2D graphite‐like layer {[Zn(PIA)H2O]⋅H2O}n (1) and an independent 1D single‐walled metal–organic nanotube (SWMONT) {[Zn2(PIA)2(bpy)2]⋅2.5 H2O⋅DMA}n (2), have been reported based on a “Y”‐shaped 5‐(pyridine‐4‐yl)isophthalic acid ligand (H2PIA). Interestingly, the 2D graphite‐like layer in 1 can transform into the independent 1D SWMONT in 2 with addition of 2,2′‐bipyridine (bpy), which represents the first successfully experimental example of an independent 1D metal–organic nanotube generated from a 2D layer by a “rolling‐up” mechanism.

Azides and Porphyrinoids: Synthetic Approaches and Applications. Part 1—Azides, Porphyrins and Corroles

“…On the other hand, organic azides revealed to be potentially green resources to transfer nitrenes, since the only by-product formed throughout the generation of nitrenes from azides is dinitrogen. Alkene aziridination and C-H amination are among the most common uses for nitrene transfer reactions, although several other very promising applications have been recently explored [95][96][97][98][99][100][101][102][103][104]. Those most recent developments employing porphyrin metal complexes as efficient catalysts are summarized below.…”

TfOH-Catalyzed N–H Insertion of α-Substituted-α-Diazoesters with Anilines Provides Access to Unnatural α-Amino Esters

“…To date, various methods have been developed to access unnatural α-amino derivatives (Scheme ). The selected existing approaches toward such privilege structures involve: (i) N -alkylation of anilines with α-bromophenylesters; (ii) transfer hydrogenation of imino esters with Hantzsch dihydropyridine by Co-phosphoric acid or Bro̷nsted acid and carboxyl-tailed benzothiazoline using a trifluoroacetic acid (TFA) catalyst; (iii) amination of aryl azides with methyl phenylacetates by Ru­(TPP)­CO or Ru­(TPP)­(py) 2 ; (iv) oxidative dehydrogenative cross-coupling of N -arylglycine esters with phenols by transition-metal catalysts (Cu, Rh, or Ru), N -substituted anilines under CuCl, and α-alkylation of N -arylglycine esters with diacyl peroxides, respectively; (v) reductive coupling of alkyl and arylglyoxylate esters with anilines using Cu/BINAP or HFIP as a catalyst; (vi) N–H insertion of sulfoxonium ylides with anilines in the presence of a catalytic amount of [Ir­(COD)­Cl] 2 or AuCl­(SMe 2 ); (vii) phosphoric acid-catalyzed C–N bond formation of sulfonium ylide esters with p -methoxyphenyl; (viii) urea-catalyzed N–H insertion–arylation of α-nitrodiazoesters with anilines; and (ix) N–H insertion of α-aryl-α-diazoacetates with anilines by transition-metal catalysts (Cu, Rh, Ru, Pd, Ir, or Fe). Despite notable progress in this area, however, among all of these methods, the use of air-sensitive metal reagents or transition-metal catalysts, harsh reaction conditions, and functional group incompatibility all have limitations; consequently, the development of a general methodology for the synthesis of unnatural α-amino esters without the use of metal reagents or transition-metal catalysts using diazo chemistry under mild reaction conditions presents a fundamental and practical challenge yet not resolved.…”

A comparative study of inter- and intramolecular C–H aminations: mechanism and site selectivity

“…[11][12][13][14] Atom-, time-, and cost-efficient opportunities have made the eld of C-H amination an active area of research. [15][16][17][18][19][20] In general, C-H amination is principally divided into two types: 7 intra- [21][22][23] and intermolecular [24][25][26] aminations. Relative to the large number of catalysts available for intramolecular amination, only a few transition-metal complexes can be employed effectively to catalyze the corresponding intermolecular reaction.…”