Preparation of Benzolactams by Pd(OAc)2-Catalyzed Direct Aromatic Carbonylation.

Abstract

ORITO*, K.; HORIBATA, A.; NAKAMURA, T.; USHITO, H.; NAGASAKI, H.; YUGUCHI, M.; YAMASHITA, S.; TOKUDA, M.; J. Am. Chem.

Room-Temperature Chemoselective Reductive Alkylation of Amines Catalyzed by a Well-Defined Iron(II) Complex Using Hydrogen

“…19 N-(4-Nitrobenzyl)propylamine (25). 47 According to the general procedure C, starting from 4-nitrobenzaldehyde (0.5 mmol, 1 equiv, 76 mg) and propylamine (0.6 mmol, 1.2 equiv, 49 μL), 25 was isolated, after purification by flash column chromatography on silica (CH 2 Cl 2 /MeOH 98/2), as a yellow oil (75 mg, 77%). 1 H NMR (CDCl 3 , 500 MHz): δ 8.17 (d, J = 8.5 Hz, 2H), 7.50 (d, J = 8.5 Hz, 2H), 3.01 (s, 2H), 2.59 (t, J = 7.1 Hz, 2H), 1.54 (sext, J = 7.2 Hz, 2H), 0.92 (t, J = 7.3 Hz, 3H) ppm.…”

Synthesis of Medium-Ring-Sized Benzolactams by Using Strong Electrophiles and Quantitative Evaluation of Ring-Size Dependency of the Cyclization Reaction Rate

“…We designed and prepared substrates 1r−x (Table 2) that bear two aromatic rings connected to a nitrogen atom, tethered by two alkyl chains of different lengths; with these compounds, the relative ratios of the products of different ring sizes can be used to evaluate the relative reaction rates of the cyclizations. 9 To estimate the size effect on ring formation rates, a solution of the substrate in dichloromethane was dropped into a mixture of TfOH and dichloromethane at 25 °C and the product ratio was determined after 1 h. All of the reactions were completed within 1 h. The main reason of the loss of starting material mass, the total product yield did not reach 100%, is that the carbamoyl cation is not only trapped by the tethered aromatic ring but also trapped by the triflate anion to afford the amine product (see Supporting Information). The intermolecular reaction was not observed based on the product analysis.…”

“…13 C NMR (100 MHz, CDCl 3 ): δ (ppm) 171. 9,149.5,147.6,131.4,129.1,112.0,108.8,55.9 (2× OMe),51.2,33.3,31.7,29.1,27.4,26.6 Synthesis of 2-Isopropyl-9,10-dimethoxy-2,3,4,5,6,7-hexahydro-1H-benzo [c]azonin-1-one (2m). To a solution of methyl 2-(( (5-(3,4dimethoxyphenyl)pentyl)(isopropyl)carbamoyl)oxy)benzoate (1m) (225 mg, 0.507 mmol) in dry dichloromethane (2.53 mL, 0.2 M), TfOH (0.45 mL, 10 equiv) was added at 0 °C.…”

Porphycene-mediated photooxidation of benzylamines by visible light

“…8,9 Porphycene-based macrocycles can be therefore considered as alternative photoactive tetrapyrrolic dyes with respect to porphyrinic compounds suitable for an efficient solar light conversion and for sensitization in catalytic photochemical reactions occurring by direct electron transfer mechanism. Experimental 2,7,12,17-Tetrapropylporphycene (1), 31 disulfonatotetrapropylporphycenes (2), 32 Sn(TPrPc)Cl 2 (3), 11, 33 5,10,15,20-tetramesitylporphyrin (4), 34 Sn(TMP)Cl 2 ( 5) 35 and N-propyl-4methoxybenzylamine (9b) 36 were prepared according to known synthetic procedures. 4-Methoxybenzylamine 6a and N-methylbenzylamine 8a were distilled before use.…”