Home Facile Synthesis of Spiro[cyclohexane-1,3’-indoline]-2,2’-diones
Article Open Access

Facile Synthesis of Spiro[cyclohexane-1,3’-indoline]-2,2’-diones

  • Shin-taro Katayama and Hiroshi Nishino EMAIL logo
Published/Copyright: December 31, 2019
Download Article (PDF)
Heterocyclic Communications
From the journal Heterocyclic Communications Volume 25 Issue 1

Abstract

Spiro[cyclohexane-1,3’-indoline]-2,2’-diones were easily prepared in good to high yields by the oxidation of N-aryl-N-methyl-2-oxocyclohexane-1-carboxamides in one pot with a short reaction time. The spiroindolinediones could be important for the total synthesis of natural products.

Keywords: spiro[cyclohexane-1,3’-indoline]-2,2’-diones; oxidative cyclization; 5-exo cyclization; radicals; heterocycles

Carbon-carbon and carbon-heteroatom bond formations are some of the most important goals in organic synthesis [1], and the second is cyclization from the point of kinetic and thermodynamic control [2]. Especially, these ingenious techniques are sometimes needed for the total synthesis of both simple and complex natural products [3,4]. For example, the C-C bond formation using boronic acid esters is well-known as a typical Suzuki-Miyaura cross-coupling reaction [5, 6, 7, 8, 9], and the cyclization using Grubbs reagents as a ring-closing metathesis (RCM) [10, 11, 12]. However, these reactions are needed to set the complicated stage for the coupling and cyclization, and sometimes under special conditions. Recently, we reported the synthesis of 3,4-dihydro-2(1H)-quinolinoes by the Mn(III)-based oxidative 6-endo-trig cyclization of 2-[2-(N-arylamino)-2-oxoethyl]malonates [13], and 3-acetylindolin-2-ones by the oxidative 5-exo-trig cyclization of N-arylbutanamides [14]. Both reactions are fully satisfied as the goal in organic synthesis, in addition, they are simple and convenient synthetic methods suitable for substituted quinolines and indoles without special conditions and techniques. In the course of these studies, we envisioned that the oxidation of N-aryl-2-oxocyclohexane-1-carboxamide might give spiro[cyclohexane-1,3’-indoline]-2,2’-diones via the formal 5-exo-trig cyclization. In order to confirm the hypothesis, N-methyl-2-oxo-N-phenylcyclohexane-1-carboxamide (1a) was prepared by the direct condensation of N-methylaniline with ethyl 2-oxocyclohexane-1-carboxylate and subjected to the Mn(III)-based oxidation.

The reaction was carried out in AcOH at room temperature using a stoichiometric amount of Mn(OAc)3. Although the oxidant was consumed for 2 days, the desired product 2a was obtained as a racemic mixture in a low yield from the reaction mixture (Scheme 1 and Table 1, Entry 1). A typical methine peak at δ 3.23 (1H, dd, J = 11.6, 5.8 Hz, H-1) and one of the ortho aromatic protons at δ 7.17 (2H, dd, J = 8.5, 1.4 Hz) in the 1H NMR spectrum of 1a disappeared in that of 2a. In addition, a typical methine carbon at δ 54.9 in the 13C NMR spectrum of 1a became a spiro quaternary carbon at δ 63.4, and furthermore, five aromatic C-H carbons of 1a reduced to four in that of 2a. These spectroscopic data clearly showed that the desired cyclization took place, that is, the product 2a should be 1’-methylspiro[cyclohexane-1,3’-indoline]-2,2’-dione [15,16]. Very recently, the same spirocyclic oxindole obtained by Cu(II)-mediated radical cross-dehydrogenative coupling using 1a was reported by Taylor et al. [17] and the spectroscopic data of 2a was in complete accordance with that of the reported compound. We were encouraged by the result, and optimized the Mn(III)-based reaction under various conditions (Entries 2-6). As a result, when the reaction was conducted using Mn(OAc)3 (2.5 eq.) in boiling AcOH, the reaction finished within only 4 min and the spiroindolinedione 2a was produced in 69% maximum yield (Entry 5) which is similar to that of Taylor et al. (65% yield) in boiling toluene for 1.5 h. In order to apply the cyclization to other substituted oxocyclohexanecarboxamides, we examined the reactions of 1b-j [18] under the optimized conditions. Gratifyingly, the results were very good as expected, giving 75-96% isolated yields of the corresponding new spiroindolinediones 2b-j (Entries 7-15).

In conclusion, a simple and convenient one-pot synthesis of spiro[cyclohexane-1,3’-indoline]-2,2’-diones 2a-j was demonstrated. The spiro compounds would be important for the total synthesis of several natural products as the starting material [19, 20, 21, 22]. The scope of the reaction using the N-aryl-2-oxocycloalkane-1-carboxamides and synthetic applications using the spiro compounds are currently underway.

Experimental

Melting points were taken using a MP-J3 Yanagimoto micromelting point apparatus and are uncorrected. The IR spectra were measured in CHCl3 or KBr using a Shimadzu 8400 FT IR spectrometer and expressed in cm−1. The NMR spectra were recorded using a JNM ECX 500 spectrometer at 500 MHz for the 1H and at 125 MHz for 13C, with tetramethylsilane as the internal standard. The chemical shifts are reported as δ values (ppm) and the coupling constants in Hz. The following abbreviations are used for the multiplicities: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; and brs, broad singlet for the NMR spectra. The high-resolution mass spectra using a JEOL JMS-700 MStation were obtained at the Instrumental Analysis Center, Kumamoto University, Kumamoto, Japan.

Scheme 1

Scheme 1

Preparation of Materials

A mixture of N-methylaniline (0.650 mL) and ethyl 2-oxocyclohexane-1-carboxylate (0.170 g) was heated under reflux for 24 h, and the crude products were separated by silica gel column chromatography eluting with EtOAc/hexane/acetone (2:7:1 v/v), giving N-methyl-2-oxo-N-phenylcyclohexane-1-carboxamide (1a) (0.126 g; 54% yield). Other 2-oxocyclohexane-1-carboxamides 1b-j were prepared according to a procedure similar to that described above. Manganese(III) acetate dihydrate, Mn(OAc)3•2H2O, was synthesized according to our modified method [14].

Table 1

Oxidation of N-Methyl-2-oxocyclohexane-1-carboxamides 1a-j with Mn(OAc)3a

EntryCarboxamide 1/1:Mn(OAc)3bTemp/°CTime/minProduct yield/%c
11a : R1 = R2 = R3 = R4 = H1:2rt2 d2a (15)
21a : R1 = R2 = R3 = R4 = H1:270702a (35)
31a : R1 = R2 = R3 = R4 = H1:210072a (48)
41a : R1 = R2 = R3 = R4 = H1:2reflux22a (60)
51a : R1 = R2 = R3 = R4 = H1:2.5reflux42a (69)
61a : R1 = R2 = R3 = R4 = H1:3reflux52a (55)
71b: R1 = R2 = R4 = H, R3 = Me1:2reflux12b (84)
81c : R1 = R2 = R4 = H, R3 = OMe1:2reflux12c (86)
91d : R1 = R2 = R4 = H, R3 = Cl1:2.5reflux12d (75)
101e : R1 = R2 = R4 = H, R3 = F1:2.5reflux12e (90)
111f : R1 = Me, R2 = R3 = R4 = H1:2reflux0.52f (96)
121g: R1 = OMe, R2 = R3 = R4 = H1:2.5reflux12g (88)
131h: R1 = Cl, R2 = R3 = R4 = H1:2.5reflux0.52h (93)
141i : R1 = R2 = Me, R3 = R4 = H1:2.5reflux12i (95)
151j : R1 = R3 = H, R2 = R4 = Me1:2.5reflux12j (88)

  1. a The reaction of the carboxamide 1 (0.5 mmol) was carried out in AcOH (15 mL).

    b Molar ratio.

    c Isolated yield.

Oxidation of 2-Oxocyclohexane-1-carboxamides 1a-j

The general procedure for the reactions of the 2-oxocyclohexane-1-carboxamides 1a-j with Mn(OAc)3•2H2O was as follows. To a cyclohexanecarboxamide 1 (0.5 mmol) dissolved in glacial AcOH (15 mL) was added Mn(OAc)3•2H2O (1 mmol), and the mixture was quickly heated under reflux using a pre-heated oil bath at 140 °C until the brown color of Mn(III) turned transparent. After the Mn(III) oxidant was completely consumed, if needed the existence of the Mn(III) could be monitored by iodine-starch paper, the solvent was removed under reduced pressure. Each reaction time is listed in Table 1. The residue was triturated with 2M HCl (15 mL) and the aqueous mixture was extracted three times with CHCl3 (20 mL × 3). The combined extracts were washed with a saturated aqueous solution of NaHCO3 and water, dried over anhydrous MgSO4, then concentrated to dryness. The obtained residue was separated by silica gel column chromatography eluting with EtOAc–hexane (3:7 v/v), giving the desired spiro[cyclohexane-1,3’-indoline]-2,2’-diones 2a-j (Table 1).

1’-Methylspiro[cyclohexane-1,3’-indoline]-2,2’-dione (2a) [17] Yield 69%; 1H NMR (500 MHz, CDCl3): δ 7.31-7.28 (2H, m, arom H), 7.09 (1H, dt, J = 7.6, 1.0 Hz, arom H), 6.84 (1H, dd, J = 8.0, 0.8 Hz, arom H), 3.18 (3H, s, =N-Me), 3.05 (1H, ddd, J = 14.3, 10.4, 5.6 Hz, H-CH), 2.59 (1H, dt, J = 14.3, 5.6 Hz, H-CH), 2.45-2.37 (1H, m, H-CH), 2.26-2.21 (1H, m, H-CH), 2.20-2.13 (1H, m, H-CH), 2.09 (1H, ddd, J = 14.1, 10.3, 4.1 Hz, H-CH), 2.02-1.94 (1H, m, H-CH), 1.89-1.82 (1H, m, H-CH); 13C NMR (125 MHz, CDCl3): δ 204.9 (C=O), 174.0 (-N-C=O), 143.0 (C-7’a), 129.2 (C-3’a), 128.4, 124.3, 122.4, 108.2 (arom CH), 63.4 (C-1), 39.5, 37.0, 26.7 (CH2), 26.2 (=N-Me), 20.1 (CH2).

1’,5’-Dimethylspiro[cyclohexane-1,3’-indoline]-2,2’-dione (2b) Yield 84%; Colorless microcrystals (from EtOH-hexane): mp 125-127 °C; IR: ν = 1690 (-N-C=O); 1H NMR (500 MHz, CDCl3): δ 7.12-7.10 (2H, m, arom H), 6.73 (1H, d, J = 8.0 Hz, arom H), 3.18 (3H, s, =N-Me), 3.07 (1H, ddd, J = 16.0, 11.0, 6.0 Hz, H-CH), 2.59 (1H, dt, J = 14.0, 5.0 Hz, H-CH), 2.44-2.40 (1H, m, H-CH), 2.36 (3H, s, Me), 2.25-2.27 (2H, m, H-CH), 2.08 (1H, ddd, J = 13.5, 10.5, 4.0 Hz, H-CH), 2.01-1.93 (1H, m, H-CH), 1.89-1.82 (1H, m, H-CH); 13C NMR (125 MHz, CDCl3): δ 205.3 (C=O), 174.1 (-N-C=O), 140.8 (C-7’a), 132.1 (C-5’), 129.4 (C-3’a), 128.9, 125.4, 108.1 (arom CH), 63.7 (C-1), 39.8, 37.3, 26.9 (CH2), 26.4 (=N-Me), 21.2 (Me), 20.3 (CH2). FAB HRMS (acetone-NBA) calcd for C15H18NO2: 244.1338 (M+H). Found: 244.1321.

5’-Methoxy-1’-methylspiro[cyclohexane-1,3’-indoline]-2,2’-dione (2c) Yield 86%; Colorless microcrystals (from EtOH-hexane): mp 111-113 °C; IR: ν = 1684 (-N-C=O); 1H NMR (500 MHz, CDCl3): δ 6.89 (1H, d, J = 2.4 Hz, arom H), 6.83 (1H, dd, J = 8.5, 2.4 Hz, arom H), 6.74 (1H, d, J = 8.5 Hz, arom H), 3.80 (3H, s, MeO), 3.17 (3H, s, =N-Me), 3.08 (1H, ddd, J = 16.0, 11.0, 6.0 Hz, H-CH), 2.57 (1H, dt, J = 14.0, 5.0 Hz, H-CH), 2.49-2.40 (1H, m, H-CH), 2.25-2.17 (2H, m, CH2), 2.08 (1H, ddd, J = 14.5, 11.0, 4.0 Hz, H-CH), 2.01-1.92 (1H, m, H-CH), 1.87-1.81 (1H, m, H-CH); 13C NMR (125 MHz, CDCl3): δ 205.1 (C=O), 173.8 (-N-C=O), 155.9 (C-5’), 136.7 (C-7’a), 130.6 (C-3’a), 112.6, 112.3, 108.6 (arom CH), 64.0 (C-1), 55.8 (MeO), 39.7, 37.5, 26.9 (CH2), 26.5 (=N-Me), 20.3 (CH2). FAB HRMS (acetone-NBA) calcd for C15H18NO3: 260.1287 (M+H). Found: 260.1296.

5’-Chloro-1’-methylspiro[cyclohexane-1,3’-indoline]-2,2’-dione (2d) Yield 75%; Colorless microcrystals (from EtOH-hexane): mp 89-91 °C; IR: ν = 1694 (-N-C=O); 1H NMR (500 MHz, CDCl3): δ 7.29 (1H, dd, J = 8.3, 2.0 Hz, arom H), 7.25 (1H, d, J = 2.0 Hz, arom H), 6.76 (1H, d, J = 8.3 Hz, arom H), 3.18 (3H, s, =N-Me), 3.10 (1H, ddd, J = 16.5, 11.5, 6.0 Hz, H-CH), 2.57 (1H, dt, J = 14.0, 5.0 Hz, H-CH), 2.50-2.42 (1H, m, H-CH), 2.25-2.19 (2H, m, CH2), 2.08 (1H, ddd, J = 15.0, 11.5, 4.0 Hz, H-CH), 2.00-1.91 (1H, m, H-CH), 1.86-1.80 (1H, m, H-CH); 13C NMR (125 MHz, CDCl3): δ 204.4 (C=O), 173.6 (-N-C=O), 141.7 (C-7’a), 130.9 (C-3’a), 128.5 (arom CH), 128.0 (C-5’), 125.2, 109.2 (arom CH), 63.7 (C-1), 39.6, 37.5, 26.9 (CH2), 26.6 (=N-Me), 20.1 (CH2). FAB HRMS (acetone-NBA) calcd for C14H15ClNO2: 264.0791 (M+H). Found: 264.0784.

5’-Fluoro-1’-methylspiro[cyclohexane-1,3’-indoline]-2,2’-dione (2e) Yield 90%; Colorless microcrystals (from EtOH-hexane): mp 76-78 °C; IR: ν = 1697 (-N-C=O); 1H NMR (500 MHz, CDCl3): δ 7.04-6.99 (2H, m, arom H), 6.77-6.75 (1H, m, arom H), 3.18 (3H, s, =N-Me), 3.12 (1H, ddd, J = 17.0, 11.5, 5.5 Hz, H-CH), 2.56 (1H, dt, J = 13.5, 4.5 Hz, H-CH), 2.52-2.43 (1H, m, H-CH), 2.25-2.19 (2H, m, CH2), 2.08 (1H, ddd, J = 15.5, 11.5, 4.0 Hz, H-CH), 2.00-1.91 (1H, m, H-CH), 1.85-1.79 (1H, m, H-CH); 13C NMR (125 MHz, CDCl3): δ 204.5 (C=O), 173.7 (-N-C=O), 159.0 (d, J = 239 Hz, C-5’), 139.0 (d, J = 3 Hz, C-7’a), 130.7 (d, J = 9 Hz, C-3’a), 114.7 (d, J = 23 Hz, C-6’), 112.8 (d, J = 23 Hz, C-4’), 108.6 (d, J = 9 Hz, C-7’), 63.8 (d, J = 1 Hz, C-1), 39.5, 37.5, 26.9 (CH2), 26.5 (=N-Me), 20.0 (CH2). FAB HRMS (acetone-NBA) calcd for C14H15FNO2: 248.1087 (M+H). Found: 248.1091.

1’,7’-Dimethylspiro[cyclohexane-1,3’-indoline]-2,2’-dione (2f) Yield 96%; Colorless microcrystals (from EtOH-hexane): mp 128-130 °C; IR: ν = 1684 (-N-C=O); 1H NMR (500 MHz, CDCl3): δ 7.09 (1H, d, J = 7.2 Hz arom H), 7.03 (1H, d, J = 7.6 Hz, arom H), 6.99 (1H, t, J = 7.6 Hz, arom H), 3.47 (3H, s, =N-Me), 3.08 (1H, ddd, J = 16.5, 11.5, 5.5 Hz, H-CH), 2.59-2.57 (1H, m, H-CH), 2.56 (3H, s, Me), 2.48-2.41 (1H, m, H-CH), 2.21-2.18 (2H, m, CH2), 2.07 (1H, ddd, J = 14.0, 10.5, 4.0 Hz, H-CH), 1.99-1.90 (1H, m, H-CH), 1.86-1.81 (1H, m, H-CH); 13C NMR (125 MHz, CDCl3): δ 205.4 (C=O), 174.8 (-N-C=O), 140.9 (C-7’a), 132.3 (arom CH), 130.0 (C-3’a), 122.5 (2C, arom CH), 119.9 (C-7’), 63.0 (C-1), 39.7, 37.7 (CH2), 29.8 (=N-Me), 26.9, 20.3 (CH2), 19.1 (Me). FAB HRMS (acetone-NBA) calcd for C15H18NO2: 244.1338 (M+H). Found: 244.1326.

7’-Methoxy-1’-methylspiro[cyclohexane-1,3’-indoline]-2,2’-dione (2g) Yield 88%; Colorless microcrystals (from EtOH-hexane): mp 94-96 °C; IR: ν = 1684 (-N-C=O); 1H NMR (500 MHz, CDCl3): δ 7.04 (1H, t, J = 7.9 Hz, arom H), 6.88 (1H, s, arom H), 6.88 (1H, d, J = 8.0 Hz, arom H), 3.84 (3H, s, MeO), 3.46 (3H, s, =N-Me), 3.10 (1H, ddd, J = 16.5, 11.0, 6.0 Hz, H-CH), 2.56 (1H, dt, J = 13.5, 4.8 Hz, H-CH), 2.50-2.41 (1H, m, H-CH), 2.23-2.19 (2H, m, CH2), 2.07 (1H, ddd, J = 14.0, 10.0, 4.0 Hz, H-CH), 1.98-1.89 (1H, m, H-CH), 1.85-1.80 (1H, m, H-CH); 13C NMR (125 MHz, CDCl3): δ 205.4 (C=O), 174.2 (-N-C=O), 145.3 (C-7’a), 131.1 (C-3’a), 130.9 (C-7’), 123.1, 117.2, 112.4 (arom CH), 63.6 (C-1), 55.9 (MeO), 39.6, 37.6 (CH2), 29.7 (=N-Me), 26.8, 20.1 (CH2). FAB HRMS (acetone-NBA) calcd for C15H18NO3: 260.1287 (M+H). Found: 260.1277.

7’-Chloro-1’-methylspiro[cyclohexane-1,3’-indoline]-2,2’-dione (2h) Yield 93%; Yellow oil; IR: ν = 1699 (-N-C=O); 1H NMR (500 MHz, CDCl3): δ 7.23 (1H, dd, J = 8.2, 1.1 Hz, arom H), 7.12 (1H, dd, J = 7.4, 1.1 Hz, arom H), 7.01 (1H, t, J = 7.5 Hz, arom H), 3.56 (3H, s, =N-Me), 3.13 (1H, ddd, J = 18.0, 12.5, 6.0 Hz, H-CH), 2.55 (1H, dt, J = 13.5, 4.3 Hz, H-CH), 2.52-2.45 (1H, m, H-CH), 2.25-2.18 (2H, m, CH2), 2.08 (1H, ddd, J = 15.5, 11.5, 4.0 Hz, H-CH), 1.97-1.88 (1H, m, H-CH), 1.84-1.78 (1H, m, H-CH); 13C NMR (125 MHz, CDCl3): δ 204.5 (C=O), 174.1 (-N-C=O), 139.0 (C-7’a), 131.9 (C-3’a), 130.8, 123.4, 123.2 (arom CH), 115.5 (C-7’), 63.2 (C-1), 39.5, 37.9 (CH2), 29.8 (=N-Me), 26.9, 20.0 (CH2). FAB HRMS (acetone-NBA) calcd for C14H15ClNO2: 264.0791 (M+H). Found: 264.0777.

1’,6’,7 ’-Trimethylspiro[cyclohexane-1, 3’-indoline]-2,2’-dione (2i) Yield 95%; Colorless microcrystals (from EtOH-hexane): mp 132-134 °C; IR: ν = 1684 (-N-C=O); 1H NMR (500 MHz, CDCl3): δ 6.99 (1H, d, J = 7.5 Hz, arom H), 6.92 (1H, d, J = 7.5 Hz, arom H), 3.49 (3H, s, =N-Me), 3.07 (1H, ddd, J = 16.5, 11.0, 5.5 Hz, H-CH), 2.56 (1H, dt, J = 14.5, 5.0 Hz, H-CH), 2.47 (3H, s, Me-C-7’), 2.45-2.38 (1H, m, H-CH), 2.30 (3H, s, Me-C-6’), 2.21-2.17 (2H, m, CH2), 2.11-2.02 (1H, m, H-CH), 1.98-1.89 (1H, m, H-CH), 1.86-1.79 (1H, m, H-CH); 13C NMR (125 MHz, CDCl3): δ 205.5 (C=O), 175.2 (-N-C=O), 141.2 (C-7’a), 138.4 (C-6’), 127.9 (C-3’a), 124.2, 121.7 (arom C), 119.1 (C-7’), 62.7 (C-1), 39.6, 37.6 (CH2), 30.6 (=N-Me), 26.8 (CH2), 20.8 (Me-C-7’a), 20.3 (CH2), 14.1 (Me-C-6’a). FAB HRMS (acetone-NBA) calcd for C16H20NO2: 258.1494 (M+H). Found: 258.1505.

1’,4’,6’-Trimethylspiro[cyclohexane-1, 3’-indoline]-2,2’-dione (2j) Yield 88%; Colorless microcrystals (from EtOH-hexane): mp 164-166 °C; IR: ν = 1686 (-N-C=O); 1H NMR (500 MHz, CDCl3): δ 6.72 (1H, s, arom H), 6.49 (1H, s, arom H), 3.19-3.15 (1H, m, H-CH), 3.13 (3H, s, =N-Me), 2.64-2.54 (2H, m, CH2), 2.38 (1H, dt, J = 13.8, 4.5 Hz, H-CH), 2.33 (3H, s, Me-C-6’), 2.27-2.22 (1H, m, H-CH), 2.17 (3H, s, Me-C-4’), 2.05-2.01 (1H, m, H-CH), 1.87-1.79 (1H, m, H-CH), 1.78-1.74 (1H, m, H-CH); 13C NMR (125 MHz, CDCl3): δ 204.6 (C=O), 173.8 (-N-C=O), 143.4 (C-7’a), 138.6 (C-6’), 134.6 (C-4’), 125.9 (arom C), 124.7 (C-3’a), 125.9 (arom C), 63.3 (C-1), 40.3, 34.8, 26.4 (CH2), 26.3 (=N-Me), 21.5 (Me-C-6’), 20.0 (CH2), 19.0 (Me-C-4’). FAB HRMS (acetone-NBA) calcd for C16H19NO2Na: 280.1313 (M+Na). Found: 280.1315.

Fax: +81-96-342-3374

Acknowledgments

This research was supported by a Grant-in-Aid for Scientific Research (C), No. 25410049, from the Japan Society for the Promotion of Science. We also acknowledge the Nissan Chemical Corporation for the financial support. HN thanks Mr. Daichi Hirata, Department of Science, Faculty of Science, Kumamoto University, Japan, for his technical assistance.

References

[1] Smith, M. B. Organic Synthesis; McGraw-Hill, Inc: New York, 1994.Search in Google Scholar

[2] Illuminati, G; Mandolini, L. Ring Closure Reactions of Bifunctional Chain Molecules. Acc. Chem. Res. 1981, 14, 95-102.10.1021/ar00064a001Search in Google Scholar

[3] Corey, E. J.; Cheng, X.-M. The Logic of Chemical Synthesis; Wiley: New York, 1989.Search in Google Scholar

[4] Nicolaou, K. C.; Sorensen, E. J. Classics in Total Synthesis; VCH: New York, 1996.Search in Google Scholar

[5] Miyaura, N.; Suzuki, A. Stereoselective Synthesis of Arylated E-Alkenes by the Reaction of Alk-1-enylboranes with Aryl Halides in the Presence of Palladium Catalyst. J. Chem. Soc., Chem. Commun. 1979, 866-867.10.1039/c39790000866Search in Google Scholar

[6] Miyaura, N.; Yanagi, T.; Suzuki, A. The palladium-catalyzed cross-coupling reaction of phenylboronic acid with haloarenes in the presence of bases. Synth. Commun. 1981, 11(7), 513-19.10.1080/00397918108063618Search in Google Scholar

[7] Miyaura, N.; Suzuki, A. Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds. Chem. Rev. 1995, 95(7), 2457-2483.10.1021/cr00039a007Search in Google Scholar

[8] Martin, R.; Buchwald, S. L. Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions Employing Dialkylbiaryl Phosphine Ligands. Acc. Chem. Res. 2008, 41, 1461-1473.10.1021/ar800036sSearch in Google Scholar PubMed PubMed Central

[9] Lennox, A. J. J.; Lloyd-Jones, G. C. Selection of boron reagents for Suzuki–Miyaura coupling. Chem. Soc. Rev. 2014, 43, 412-443.10.1039/C3CS60197HSearch in Google Scholar

[10] Trnka, T. M.; Grubbs, R. H. The Development of L2X2RudCHR Olefin Metathesis Catalysts: An Organometallic Success Story. Acc. Chem. Res. 2001, 34, 18-29.10.1021/ar000114fSearch in Google Scholar PubMed

[11] Deiters, A.; Martin, S. F. Synthesis of Oxygen- and Nitrogen-Containing Heterocycles by Ring-Closing Metathesis. Chem. Rev. 2004, 104, 2199-2238.10.1021/cr0200872Search in Google Scholar PubMed

[12] Monfette, S.; Fogg, D. E. Equilibrium Ring-Closing Metathesis. Chem. Rev. 2009, 109, 3783–3816.10.1021/cr800541ySearch in Google Scholar PubMed

[13] Tsubusaki, T.; Nishino, H. Manganese(III)-mediated facile synthesis of 3,4-dihydro-2(1H-quinolinones: selectivity of the 6-endo and 5-exo cyclization. Tetrahedron 2009, 65, 9448-9459.10.1016/j.tet.2009.08.068Search in Google Scholar

[14] Kikue, N.; Takahashi, T.; Nishino, H. Mn(III)-Based Oxidative Cyclization of N-Aryl-3-oxobutanamides. Facile Synthesis and Transformation of Substituted Oxindoles. Heterocycles 2014, 90, 540-562.10.3987/COM-14-S(K)57Search in Google Scholar

[15] Flann, C. J.; Overman, L. E.; Sarkar, A. K. Synthesis of 3-Acyl-3-alkyloxindoles. Tetrahedron Lett. 1991, 32, 6993-6996.10.1016/0040-4039(91)85022-WSearch in Google Scholar

[16] Wang,L.; Su, Y.; Xu, X.; Zhang, W. A Comparison of the Photosensitized Rearrangement and the Lewis-Acid-Catalyzed Rearrangement of Spirooxindole Epoxides. Eur. J. Org. Chem. 2012, 6606-6611.10.1002/ejoc.201201020Search in Google Scholar

[17] Hurst, T. E.; Gorman, R.; Drouhin, P.; Taylor, R. J. K. Application of copper(II)-mediated radical cross-dehydrogenative coupling to prepare spirocyclic oxindoles and to a formal total synthesis of Satavaptan. Tetrahedron 2018, 74, 6485-6496.10.1016/j.tet.2018.09.026Search in Google Scholar

[18] Although we described the starting materials 1b-j as an oxocyclohexanecarboxamide form in Scheme 1, ortho-substituted N-aryl-oxocyclohexanecarboxamides 1f-i existed as an enamine form in CDCl3 based on their NMR spectra (see Supporting Information).Search in Google Scholar

[19] Flann, C. J.; Overman, L. E.; Sarkar, A. K. Synthesis of 3-Acyl-3-alkyloxindoles. Tetrahedron Lett. 1991, 32(48), 6993-6996.10.1016/0040-4039(91)85022-WSearch in Google Scholar

[20] Atarashi, S.; Choi, J.-K.; Ha, D.-C.; Hart, D. J.; Kuzmich, D. Lee, C.-S.; Ramesh, S.; C. Wu, S.C. Free Radical Cyclizations in Alkaloid Total Synthesis: (±)-21-Oxogelsemine and (±)-Gelsemine, J. Am. Chem. Soc. 1997, 119, 6226-6241.10.1021/ja970089hSearch in Google Scholar

[21] Madin, A.; O’Donnell, C. J.; Oh, T.; Old, D. W.; Overman, L. E.; Sharp M. J. Use of the Intramolecular Heck Reaction for Forming Congested Quaternary Carbon Stereocenters. Stereocontrolled Total Synthesis of (±)-Gelsemine. J. Am. Chem. Soc. 2005, 127, 18054-18065.10.1021/ja055711hSearch in Google Scholar PubMed PubMed Central

[22] Venkatesan, H.; Davis, M. C.; Altas, Y.; Snyder, J. P.; Liotta, D. C. Total Synthesis of SR 121463 A, a Highly Potent and Selective Vasopressin V2 Receptor Antagonist. J. Org. Chem. 2001, 66, 3653-3661.10.1021/jo0004658Search in Google Scholar PubMed

Received: 2019-01-22
Accepted: 2019-06-03
Published Online: 2019-12-31

© 2019 Katayama and Nishino, published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 Public License.

Articles in the same Issue

  1. Research Article
  2. Magnesium porphyrazine with peripheral methyl (3,5-dibromophenylmethyl)amino groups – synthesis and optical properties
  3. Synthesis and fungicidal activity of novel imidazo[4, 5-b]pyridine derivatives
  4. Synthesis of indazolo[5,4-b][1,6]naphthyridine and indazolo[6,7-b][1,6]naphthyridine derivatives
  5. Zinc Chloride Catalyzed Amino Claisen Rearrangement of 1-N-Allylindolines: An Expedient Protocol for the Synthesis of Functionalized 7-Allylindolines
  6. Synthesis and Biological Evaluation of (E)-N’-Benzylidene-7-methyl-2-propyl-1H-benzo[d] imidazole-5-carbohydrazides as Antioxidant, Anti-inflammatory and Analgesic agents
  7. Efficient synthesis, reactions and spectral characterization of pyrazolo[4’,3’:4,5]thieno[3,2-d] pyrimidines and related heterocycles
  8. Asymmetric Mannich Reaction: Synthesis of Novel Chiral 5-(substituted aryl)-1,3,4-Thiadiazole Derivatives with Anti-Plant-Virus Potency
  9. Synthesis and antitubercular activity of new N-[5-(4-chlorophenyl)-1,3,4-oxadiazol-2-yl]-(nitroheteroaryl)carboxamides
  10. Remarkable electronic effect on the total stereoselectivity of the cycloaddition reaction of arylnitrile oxides with pyrrol-2-one derivatives
  11. Preliminary Communications
  12. Crystal structure and molecular docking studies of new pyrazole-4-carboxamides
  13. Research Article
  14. Synthesis of polycyclic phosphonates via an intramolecular Diels-Alder reaction of 2-benzoylbenzalaldehyde and alkenyl phosphites
  15. Asymmetric total synthesis of filamentous fungi related resorcylic acid lactones 7-epi-zeaenol and zeaenol
  16. The first in situ synthesis of 1,3-dioxan-5-one derivatives and their direct use in Claisen-Schmidt reactions
  17. Synthesis and fungicidal activities of perfluoropropan-2-yl-based novel quinoline derivatives
  18. Combined XRD-paramagnetic 13C NMR spectroscopy of 1,2,3-triazoles for revealing copper traces in a Huisgen click-chemistry cycloaddition. A model case
  19. Cytotoxic and antimicrobial activities of some novel heterocycles employing 6-(1,3-diphenyl-1H-pyrazol-4-yl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile
  20. Substrate-controlled Diastereoselective Michael Addition of Alkylidene Malonates by Grignard Reagents
  21. Synthesis of 1,2,3 triazole-linked benzimidazole through a copper-catalyzed click reaction
  22. Synthesis and spectral characteristics of N-(1-([1,2,4]triazolo[3,4-b][1,3,4]thiadiazol-6-ylamino)-2,2,2-trichloroethyl)carboxamides
  23. Facile One-pot Protocol of Derivatization Nitropyridines: Access to 3-Acetamidopyridin-2-yl 4-methylbenzenesulfonate Derivatives
  24. Naphthalene substituted benzo[c]coumarins: Synthesis, characterization and evaluation of antibacterial activity and cytotoxicity
  25. A Green Synthesis and Antibacterial Activity of N-Arylsulfonylhydrazone Compounds
  26. Preliminary Communications
  27. Facile Synthesis of Spiro[cyclohexane-1,3’-indoline]-2,2’-diones
  28. Research Article
  29. Synthesis and AChE inhibitory activity of N-glycosyl benzofuran derivatives
  30. [DMImd-DMP]: A highly efficient and reusable catalyst for the synthesis of 4H-benzo[b]pyran derivatives
https://doi.org/10.1515/hc-2019-0022
Keywords for this article
spiro[cyclohexane-1,3’-indoline]-2,2’-diones; oxidative cyclization; 5-exo cyclization; radicals; heterocycles
Creative Commons
BY 4.0

Articles in the same Issue

  1. Research Article
  2. Magnesium porphyrazine with peripheral methyl (3,5-dibromophenylmethyl)amino groups – synthesis and optical properties
  3. Synthesis and fungicidal activity of novel imidazo[4, 5-b]pyridine derivatives
  4. Synthesis of indazolo[5,4-b][1,6]naphthyridine and indazolo[6,7-b][1,6]naphthyridine derivatives
  5. Zinc Chloride Catalyzed Amino Claisen Rearrangement of 1-N-Allylindolines: An Expedient Protocol for the Synthesis of Functionalized 7-Allylindolines
  6. Synthesis and Biological Evaluation of (E)-N’-Benzylidene-7-methyl-2-propyl-1H-benzo[d] imidazole-5-carbohydrazides as Antioxidant, Anti-inflammatory and Analgesic agents
  7. Efficient synthesis, reactions and spectral characterization of pyrazolo[4’,3’:4,5]thieno[3,2-d] pyrimidines and related heterocycles
  8. Asymmetric Mannich Reaction: Synthesis of Novel Chiral 5-(substituted aryl)-1,3,4-Thiadiazole Derivatives with Anti-Plant-Virus Potency
  9. Synthesis and antitubercular activity of new N-[5-(4-chlorophenyl)-1,3,4-oxadiazol-2-yl]-(nitroheteroaryl)carboxamides
  10. Remarkable electronic effect on the total stereoselectivity of the cycloaddition reaction of arylnitrile oxides with pyrrol-2-one derivatives
  11. Preliminary Communications
  12. Crystal structure and molecular docking studies of new pyrazole-4-carboxamides
  13. Research Article
  14. Synthesis of polycyclic phosphonates via an intramolecular Diels-Alder reaction of 2-benzoylbenzalaldehyde and alkenyl phosphites
  15. Asymmetric total synthesis of filamentous fungi related resorcylic acid lactones 7-epi-zeaenol and zeaenol
  16. The first in situ synthesis of 1,3-dioxan-5-one derivatives and their direct use in Claisen-Schmidt reactions
  17. Synthesis and fungicidal activities of perfluoropropan-2-yl-based novel quinoline derivatives
  18. Combined XRD-paramagnetic 13C NMR spectroscopy of 1,2,3-triazoles for revealing copper traces in a Huisgen click-chemistry cycloaddition. A model case
  19. Cytotoxic and antimicrobial activities of some novel heterocycles employing 6-(1,3-diphenyl-1H-pyrazol-4-yl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile
  20. Substrate-controlled Diastereoselective Michael Addition of Alkylidene Malonates by Grignard Reagents
  21. Synthesis of 1,2,3 triazole-linked benzimidazole through a copper-catalyzed click reaction
  22. Synthesis and spectral characteristics of N-(1-([1,2,4]triazolo[3,4-b][1,3,4]thiadiazol-6-ylamino)-2,2,2-trichloroethyl)carboxamides
  23. Facile One-pot Protocol of Derivatization Nitropyridines: Access to 3-Acetamidopyridin-2-yl 4-methylbenzenesulfonate Derivatives
  24. Naphthalene substituted benzo[c]coumarins: Synthesis, characterization and evaluation of antibacterial activity and cytotoxicity
  25. A Green Synthesis and Antibacterial Activity of N-Arylsulfonylhydrazone Compounds
  26. Preliminary Communications
  27. Facile Synthesis of Spiro[cyclohexane-1,3’-indoline]-2,2’-diones
  28. Research Article
  29. Synthesis and AChE inhibitory activity of N-glycosyl benzofuran derivatives
  30. [DMImd-DMP]: A highly efficient and reusable catalyst for the synthesis of 4H-benzo[b]pyran derivatives
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 11.9.2025 from https://www.degruyterbrill.com/document/doi/10.1515/hc-2019-0022/html
Scroll to top button