Iron Pentacarbonyl in Alkoxy- and Aminocarbonylation of Aromatic Halides

Abstract

We have identified reaction conditions for a Heck-type carbonylation based on [Fe(CO)₅]. Preliminary optimization of alkoxycarbonylation on 2-bromonaphthalene defined functioning composition of the reaction mixture which was then applied on a small set of (hetero)aromatic halides. Respective aminocarbonylation of these halides with different amines, including aniline and benzotriazole, was accomplished with reasonable results.

Key words

aminocarbonylation - methoxycarbonylation - carbonylation - carbonyl complexes - iron - palladium catalysis

• References and Notes

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• 11 General Procedure for the Carbonylation of Aryl Halides An aryl bromide (1 mmol), Ph₃P (94 mg, 0.36 mmol), and Pd(OAc)₂ (22 mg, 0.1 mmol) were weighed into screw cap vial equipped with a magnetic stir bar. Dry MeCN (5 mL) was added, followed by Et₃N (2.5 mL) and the corresponding amine (1.5 mmol). Neat iron pentacarbonyl (35 μL, 0.25 mmol) was added, and the vial was thoroughly closed and heated in the preheated oil bath or aluminum heating block (80 °C). The reaction mixture was stirred at the specified temperature for 23 h, then concentrated with approximately 1 g of silica, and the absorbed material was purified by gradient MPLC (hexanes–EtOAc in ratios 1:10 to 1:1). Methyl and n-butyl carboxylates, described in the article, were prepared in a similar manner; a mixture of MeCN with MeOH or n-BuOH in a ratio of 2:1 was used instead of pure MeCN, the identical amount of dppf (0.36 mmol) was used instead of Ph₃P in specified cases. Methyl Naphthalene-2-carboxylate (2) The compound was prepared according to the described general procedure with dppf as the ligand additive from 2-bromonaphthalene (1, 1.035 g, 5 mmol) of, isolated as a colorless oil (661 mg, 71%). All data, including ¹H NMR, ¹³C NMR, LC–MS, and TLC data were identical with physical sample of 2, purchased from Sigma-Aldrich. n-Butyl Naphthalene-2-carboxylate (3) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 1 (150 mg, 0.72 mmol), isolated as an off-white solid (164 mg, 52%). ¹H NMR, ¹³C NMR, IR, ESI-MS, and TLC data of isolated 3 were in accordance with published data;^12a mp 40–45 °C (EtOAcOEt); lit.:^12b mp 41 °C. Methyl Pyridine-2-carboxylate (5) The compound was prepared according to the described general procedure with dppf as the ligand additive from 2-bromopyridine (4a, 150 mg, 0.95 mmol), isolated as a pale yellow oil (33 mg, 25%). HPLC yield in the reaction mixture was 90% according to the 254 nm peak-area calibration curve made from purchased sample. All data, including ¹H NMR, ¹³C NMR, LC–MS, and TLC data were identical with physical sample of 5, purchased from Sigma-Aldrich. The isolated sample was slightly colored in contrast with colorless commercial one. n-Butyl Pyridine-2-carboxylate (6) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 4a (150 mg, 0.95 mmol), isolated as a pale yellow oil (66 mg, 39%). All data, including ¹H NMR, ¹³C NMR, IR, ESI-MS, and TLC data were in accordance with the literature data.¹³ Methyl Quinoline-3-carboxylate (9) The compound was prepared according to the described general procedure with dppf as the ligand additive from 3-bromoquinoline (8, 250 mg, 1.2 mmol), isolated as an off-white solid (90 mg, 40%). NMR and IR data were identical with the literature data;¹⁴ mp 74–77 °C (EtOAc–hexanes); lit.:¹⁴ mp 75–77 °C. n-Butyl Quinoline-3-carboxylate (10) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 8 (146 mg, 0.7 mmol), isolated as a thick yellow oil (140 mg, 87%). ¹H NMR, ¹³C NMR, and IR data were in accordance with the literature data.¹⁴ N-Phenyl-2-naphthamide (12) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 2-bromonaphthalene (1, 207 mg, 1 mmol), isolated as an off-white solid (198 mg, 80%); mp 166–168 °C (EtOAc); lit.:^15b 170–171 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.16 (br t, 1 H, J = 7.4 Hz), 7.38 (br t, 2 H, J = 7.9 Hz), 7.51–7.62 (m, 2 H), 7.70 (d, 2 H, J = 7.7 Hz, Ph), 7.85–7.95 (m, 4 H), 8.07 (br s, 1 H), 8.36 (s, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 120.3, 123.5, 124.6, 126.9, 127.5, 127.8, 127.9, 128.7, 128.9, 129.1 (all d), 132.2, 132.6, 134.8, 138.0 (all s), 165.8 (s). IR spectra were in agreement with the literature data.^15a NMR in DMSO can be found there as well. ESI-HRMS: m/z calcd for C₁₇H₁₃NO + H [M + 1]: 248.1070; found: 248.1078. N-Benzyl-2-naphthamide (14) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 2-bromonaphthalene (1, 207 mg, 1 mmol), isolated as an off-white solid (220 mg, 84%). Spectral data (NMR, IR, MS) were in agreement with the literature data;^2m mp 140–142 °C (EtOAc); lit.:^15a mp 138–139 °C. N,N-Diethyl-2-naphthamide (16) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 2-bromonaphthalene (1, 207 mg, 1 mmol), isolated as a thick colorless oil (98 mg, 43%). All NMR and IR data were in accordance with the literature data.¹⁶ N,N-Diethylpicolinamide (17) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 2-bromopyridine (4a, 158 mg, 1 mmol), isolated as a pale yellow oil (137 mg, 77%). All properties were in full accordance with the literature data.¹⁷ N-Phenyl-2-pyridinecarboxamide (18) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 4a (158 mg, 1 mmol), isolated as a yellowish solid (141 mg, 71%). All spectral data were in accordance with the literature data;^18a mp 74–76 °C (EtOAc–hexanes); lit.^18b mp 74–75 °C. N-Benzyl-2-pyridinecarboxamide (19) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from bromide 4a (158 mg, 1 mmol) or from chloride 4b (114 mg, 1 mmol), isolated in both cases as a pale brown solid (98 mg, 46% from bromide 4a, 68 mg, 32% from chloride 4b). All spectral data were in agreement with the literature data;¹⁹ mp 81–83 °C (EtOAc–hexanes); lit.¹⁹ mp 81–84 °C. N-Benzyl-4-pyridinecarboxamide (21) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 4-bromopyridine (20, 158 mg, 1 mmol), isolated as an off-white solid (132 mg, 62%); mp 86–88 °C (EtOAc–hexanes; lit.^20b mp 87–88 °C. ¹H NMR (300 MHz, CD₃OD): δ = 4.58 (s, 2 H), 7.34 (br s, 5 H), 7.82 (br s, 2 H), 8.71 (br s, 2 H), in rough agreement with the literature data.^{20a 13}C NMR (75 MHz, CD₃OD): δ = 44.7 (t), 123.2 (d, 2 C), 128.4, 128.7, 129.6 (all d), 139.7 (s), 143.9 (s), 151.0 (d, 2 C), 167.6 (s). IR (ATR): ν = 3300, 3064, 1645, 1542, 1196, 1172, 1126, 723, 660 cm^–1. ESI-HRMS: m/z calcd for C₁₃H₁₂N₂O + H [M + 1]: 213.1022; found: 213.1018. 2-Benzyl-3-iminoisoindolin-1-one (23) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 2-bromobenzonitrile (22, 182 mg, 1 mmol), isolated as an off-white solid (168 mg, 71%); mp 123–124 °C (EtOAc); lit.^10b mp 122–123 °C. NMR spectra were in accordance with the literature data.^10b IR spectra were in accordance with the literature.^10a ESI-HRMS: m/z calcd for C₁₅H₁₂N₂O + H [M + 1]: 237.1022; found: 237.1019. N-Benzyl-4-cyanobenzamide (25) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 4-bromobenzonitrile (24, 182 mg, 1 mmol), isolated as an off-white solid (203 mg, 86%); mp 150–153 °C (EtOAc–hexanes); lit.^21b mp 151 °C. ¹H NMR (300 MHz, CDCl₃): δ = 4.61 (d, 2 H, J = 5.7 Hz), 6.82 (br s, 1 H), 7.17–7.38 (m, 5 H), 7.67 (d, 2 H, J = 8.1 Hz), 7.87 (d, 2 H, J = 8.1 Hz), in fair accordance with the literature data.^{21a 13}C NMR (75 MHz, CDCl₃): δ = 44.3 (t), 115.0, 117.9 (all s), 127.2, 127.7, 127.8, 128.6, 128.8, 132.3 (all d), 137.5, 138.2 (all s), 165.6 (s). IR (ATR): ν = 3309, 3030, 2233, 1643, 1548, 1494, 1311, 719, 672 cm^–1. ESI-HRMS: m/z calcd for C₁₅H₁₂N₂O + H [M + 1]: 237.1022; found: 237.1018. N-Benzyl-4-methoxybenzamide (27) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 4-bromoanisole (26, 187 mg, 1 mmol), isolated as a white solid (123 mg, 51%). Spectral data were in accordance with the literature data;^2m mp 128–130 °C (EtOAc–hexanes); lit.²² mp 129–130 °C. N-Benzylquinoline-2-carboxamide (29) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 2-bromoquinoline (28, 208 mg, 1 mmol), isolated as a white solid (228 mg, 87%). Spectral data were in full accordance with the literature data;^2m mp 125–127 °C (EtOAc); lit.:^2m 124–125 °C. N-Benzylquinoline-3-carboxamide (30) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from 3-bromoquinoline (8, 208 mg, 1 mmol), isolated as a white solid (165 mg, 63%); mp 140–141 °C (EtOAc); lit.:^2c 140 °C. NMR and IR data were in rough agreement with the literature data.^{2c 1}H NMR (300 MHz, CDCl₃): δ = 4.69 (d, 2 H, J = 5.7 Hz), 6.94 (br s, 1 H), 7.22–7.40 (m, 5 H), 7.58 (ddd, 1 H, J = 1.0, 7.0, 8.0 Hz), 7.77 (ddd, 1 H, J = 1.4, 7.0, 8.4 Hz), 7.83 (br d, 1 H, J = 8.1 Hz, H-5), 8.10 (br d, 1 H, J = 8.4 Hz), 8.59 (br d, 1 H, J = 2.0 Hz), 9.26 (d, J = 2.2 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 44.2 (t), 126.8 (s), 127.5 (d), 127.7 (d), 128.0 (s), 128.7, 128.8, 129.3, 131.2, 135.6 (all d), 137.8 (s), 148.1 (d), 149.2 (s), 165.5 (s). IR (ATR): ν = 3257, 3059, 3028, 1659, 1620, 1542, 1500, 1430, 1302, 1250 740, 692 cm^–1. ESI-HRMS: m/z calcd for C₁₇H₁₄N₂O + H [M + 1]: 263.1179; found: 263.1170. 1-(2-Naphthoyl)benzotriazole (32) The compound was prepared according to the described general procedure with Ph₃P as the ligand additive from naphthalene 1 (207 mg, 1 mmol), isolated as a pale brown solid (98 mg, 36%). Spectral data were in full agreement with the literature data;^23a mp 137–139 °C (EtOAc); lit.^23b mp 140–142 °C.
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