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DOI: 10.1055/s-0043-1775472
Claisen-Type Condensation of Ketones with Carboxylic Acids: Synthesis of α,α-Disubstituted β-Keto Carbonyl Compounds
We thank the Fundamental Research Funds for the Central Universities for financial support.
Abstract
A novel and efficient Claisen-type condensation reaction for the synthesis of α,α-disubstituted β-keto carbonyl compounds from ketones and unactivated carboxylic acids in a P2O5/Tf2O system is presented. This approach can be applied to reactions between various open-chain ketones, cyclopentanones, indenones, and tetrahydronaphthones and unactivated alkyl carboxylic acids, aromatic carboxylic acids, and unsaturated carboxylic acids, affording all-carbon spirocyclic 1,3-diketones of various sizes and acyclic 1,3-diketones containing all-carbon quaternary centers in moderate to high yields. Furthermore, we have also confirmed that the reaction proceeds via an enol lactone intermediate.
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Key words
Claisen-type condensation - α,α-disubstituted β-keto carbonyl compounds - ketones - carboxylic acids - P2O5/Tf2OClaisen condensation and its intramolecular variant, the Dieckmann condensation, are fundamental and useful C–C bond-forming reactions in organic synthesis.[1] The Claisen and Dieckmann condensations occur between an ester and another carbonyl compound containing an α-proton and typically require high temperatures[2] and the presence of strong base reagents (e.g., MOR, LDA, MHMDS, MH; M = Li, Na, K) to afford a β-keto carbonyl compound.[1c] [3] In the classical Claisen condensation reaction, the enol ester nucleophiles and the carboxylic ester electrophilic reagents undergo reversible addition and elimination sequences. Subsequently, irreversible deprotonation occurs at the α-position of the β-keto ester, shifting the equilibrium towards the condensation product (Scheme [1a]).[3d,4] Although the Claisen condensation has been an effective reaction to obtain β-keto carbonyl compounds by C–C bond formation for over a century, there are still some limitations: (i) a general crossed condensation between two different esters, each of which possesses α-hydrogens, generally affords all four products;[5] (ii) the Claisen condensation reaction typically requires activated carboxylic acids as substrates (e.g., esters, acid chlorides) or the presence of enolate precursors (e.g., enol silyl ethers, ketene silyl acetals, ketene silyl thioacetals);[5e] [f] [6] (iii) formation of α,α-disubstituted β-keto carbonyl compounds via the Claisen condensation under basic conditions is challenging due to the lack of the ability to form stable disubstituted ester enolates (Scheme [1b]).[3d] [7]
All-carbon 1,3-diketones as key building blocks in organic syntheses exhibit a broad range of biological activities and applications.[8] To date, though many methods have been proposed, it is noticeable that only limited strategies have been established to access these useful building blocks from carboxylic acids.[9] The Claisen-type condensation of ketones with unactivated carboxylic acids under mild conditions to give all-carbon quaternary center 1,3-diketones remains unknown. Thus, exploration of more direct and efficient condensation conditions to prepare single α,α-disubstituted β-keto carbonyl compounds is still necessary and urgent.
Herein, we have developed a novel and direct Claisen-type condensation reaction for the first time, which can effectively avoid cross-condensation side reactions, to obtain a desired single α,α-disubstituted β-keto carbonyl compound (Scheme [1c]) that is difficult to obtain via the Claisen condensation under basic conditions. We have assessed various sizes of all-carbon spirocyclic 1,3-diketone compounds by Dieckmann-type condensation using ketones with unactivated carboxylic acids as the reaction substrates, and have obtained acyclic all-carbon quaternary center 1,3-diketones by Claisen-type condensation of ketones with commercial carboxylic acids.
To begin our investigation, carboxylic acid 1a was selected as a model substrate to identify suitable condensation conditions. Pleasingly, the initial attempt with P2O5 (2.0 equiv) in CHCl3 at room temperature successfully afforded the desired product, spiro[4.4]nonane-1,6-dione (2a), in 15% yield (Table [1], entry 1). When an equivalent amount of TfOH (2.0 equiv) was used instead of P2O5, we also obtained the target product in 10% yield (Table [1], entry 2). Meanwhile, a slight increase in yield was observed when the amount of TfOH was reduced to 1.0 equivalent (Table [1], entry 3). Surprisingly, adding P2O5 (2.0 equiv) and TfOH (1.0 equiv) together to the reaction system, which effectively promoted the condensation, furnished the desired product with a yield of 38% (Table [1], entry 4). As a promising yield of the reaction was observed under the catalysis of P2O5/TfOH, we screened other proton acids, anhydrides, and equivalents of protic acids under this reaction system (Table [1], entries 5–11). It was found that the reaction using P2O5 (2.0 equiv) and Tf2O (0.1 equiv) in CHCl3 could produce 2a in an enhanced yield of 53% (Table [1], entry 9). Next, evaluation of various other solvents (Table [1], entries 12–15) revealed that DCM provided the best yield (Table [1], entry 14).
a Reaction conditions, unless otherwise noted: 1a (0.2 mmol), P2O5 (0.4 mmol), HA/anhydride, solvent (2.0 mL), room temperature.
b Isolated yield.
c Addition without proton acid or anhydride.
d Addition without P2O5.
Under the optimized reaction conditions, the scope of α-substituted cyclic ketones containing a terminal carboxyl group was then explored (Scheme [2]). Various sizes of spirocyclic 1,3-diketone compounds were obtained under the optimal cyclization conditions with moderate to high yields from various α-substituted cyclic ketones and carboxylic acid chains of different lengths. We found that the conditions can be well-applied to spirocyclic 1,3-diketones containing five- or six-membered rings (2a, 2b, 2d, 2e), but only ca. 50% yield was obtained for spirocyclic 1,3-diketones containing seven-membered rings (2c, 2f, 2g, 2h, 2i). Generally, carboxylic acid substrates derived from 1-indanone with either an electron-withdrawing or electron-donating substituent at the 5- or 6-position produced the spiro[4.4]tricyclic β-diketones in moderate yields (2j–2m). In addition, either electron-donating or electron-withdrawing spirobiindanones could also be obtained in good yields using this approach (2n–2p).
Subsequently, we investigated the applicability of the P2O5/Tf2O system for intermolecular reactions of α-substituted ketones and carboxylic acids (Scheme [3]). Generally, a wide array of carboxylic acids, ranging from alkyl carboxylic acids, aromatic carboxylic acids, to unsaturated carboxylic acids, react with α-methyl-1-indenone to yield various 1,3-dicarbonyl compounds containing an all-carbon quaternary center (5a–5g). The configuration of 5d was confirmed through X-ray crystallography.[10]
For α-methyltetrahydronaphthone, when reacted with phenylacetic acid, compound 5n was obtained in 47% yield. Similarly, compound 5o was obtained in 53% yield by reaction with phenylpropanoic acid. α-Substituted cyclopentanone can also react with phenylacetic acid. In this system, phenylpropanoic acids substituted at the C4′-position with groups such as methyl, methoxy, and fluorine gave the corresponding 1,3-dicarbonyl compounds 5h–5m in 38–57% yield. Both electron-donating and electron-withdrawing groups on the phenylpropanoic acid were compatible with this reaction. Acyclic ketones were next studied, and we discovered that this reaction is also applicable to reactions between various acyclic ketones and carboxylic acids, providing various 1,3-dicarbonyl compounds (5p–5x).
An enol lactone compound was obtained in 54% yield using carboxylic acid 1m as the substrate in the P2O5/Tf2O system (Scheme [4]). Reaction of the enol lactone continued in this system, and finally, the target compound 2m was isolated. Based on these results, we conclude that the condensation proceeds through enol lactone Int. 1, whose structure was determined by single-crystal X-ray diffraction.[11]
In conclusion, we have developed a P2O5/Tf2O-mediated Claisen-type condensation reaction of ketones with unactivated carboxylic acids, providing a novel and effective approach for the synthesis of single α,α-disubstituted β-keto carbonyl compounds. This approach can effectively avoid cross-condensation side reactions and is amenable to a wide range of indenones, tetrahydronaphthones, cyclopentanones, and open-chain ketones with unactivated alkyl carboxylic acids, aromatic carboxylic acids, and unsaturated carboxylic acids, enabling the synthesis of diverse all-carbon spirocyclic 1,3-diketones with various ring sizes and acyclic all-carbon quaternary center containing 1,3-diketones.
In addition to commercially available extra dry solvents, all solvents were purified by standard operating methods. THF was distilled from sodium; dichloromethane (DCM) and 1,2-dichloroethane (DCE) were distilled from calcium hydride. All reactions under standard conditions were monitored by TLC on silica gel F254 plates. Silica gel (200–300 mesh), petroleum ether (bp 60–90 °C), and EtOAc were used for product purification by flash column chromatography. 1H NMR spectra were acquired on a Bruker 400 instrument; 13C NMR spectra were acquired at 101 MHz. Chemical shifts (δ) are reported in ppm relative to residual solvent signals (CDCl3: 7.27 ppm for 1H NMR, 77.0 ppm for 13C NMR). The following abbreviations are used to indicate the multiplicity in NMR spectra: s, singlet; d, doublet; t, triplet; q, quartet; dd, double of doublets; td, triplet of doublets; m, multiplet. High-resolution mass spectral analysis (HRMS) data were determined on an APEXII 47e FT-ICR spectrometer by means of the ESI technique. X-ray diffraction data were collected on an Agilent SuperNova Eos diffractometer.
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Spirocyclic 1,3-Diketones 2a–2p; General Procedure
To a solution of carboxylic acid derivative 1a–1p (0.2 mmol, 1.0 equiv) in DCM (2.0 mL) was added P2O5 (0.4 mmol, 2.0 equiv) and Tf2O (0.02 mmol, 0.1 equiv) at room temperature and the reaction mixture was stirred at that same temperature until complete consumption of carboxylic acid as detected by TLC. The solution was then quenched with saturated NaHCO3 and extracted with DCM (3 × 5 mL). The combined organic layer was washed with brine (20 mL), dried over anhydrous Na2SO4, and evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel to afford the spirocyclic 1,3-diketone 2a–2p.
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Spiro[4.4]nonane-1,6-dione (2a)
White solid; yield: 19.2 mg (63%).
1H NMR (400 MHz, CDCl3): δ = 2.43–2.28 (m, 6 H), 2.24–2.12 (m, 2 H), 1.95–1.87 (m, 2 H), 1.85–1.78 (m, 2 H).
13C NMR (101 MHz, CDCl3): δ = 216.8, 64.4, 38.5, 34.3, 19.8.
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Spiro[4.5]decane-1,6-dione (2b)
Colorless liquid; yield: 17.2 mg (52%).
1H NMR (400 MHz, CDCl3): δ = 2.73–2.63 (m, 2 H), 2.47–2.40 (m, 1 H), 2.31 (td, J = 7.6, 1.8 Hz, 2 H), 2.16–2.07 (m, 1 H), 2.06–1.96 (m, 2 H), 1.94–1.85 (m, 2 H), 1.79–1.71 (m, 1 H), 1.68–1.54 (m, 3 H).
13C NMR (101 MHz, CDCl3): δ = 215.8, 208.2, 64.4, 39.8, 38.5, 35.9, 33.7, 26.7, 21.0, 19.0.
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Spiro[4.6]undecane-1,6-dione (2c)
Yellow liquid; yield: 17.3 mg (48%).
1H NMR (400 MHz, CDCl3): δ = 2.89 (td, J = 11.6, 2.6 Hz, 1 H), 2.69–2.64 (m, 1 H), 2.45–2.38 (m, 1 H), 2.36–2.23 (m, 2 H), 2.13–1.99 (m, 2 H), 1.92–1.77 (m, 4 H), 1.73–1.64 (m, 2 H), 1.58–1.44 (m, 2 H), 1.30–1.23 (m, 1 H).
13C NMR (101 MHz, CDCl3): δ = 216.4, 210.6, 67.8, 41.9, 38.4, 34.0, 33.5, 30.4, 26.3, 25.5, 19.2.
HRMS (ESI): m/z calcd for C11H16O2 [M + H]+: 181.1223; found: 181.1220.
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Spiro[4.5]decane-1,6-dione (2d)
Colorless liquid; yield: 20.3 mg (61%).
1H NMR (400 MHz, CDCl3): δ = 2.73–2.64 (m, 2 H), 2.44 (dt, J = 15.1, 5.2 Hz, 1 H), 2.33–2.29 (m, 2 H), 2.17–2.11 (m, 1 H), 2.08–1.96 (m, 2 H), 1.95–1.86 (m, 2 H), 1.80–1.69 (m, 1 H), 1.67–1.54 (m, 3 H).
13C NMR (101 MHz, CDCl3): δ = 215.7, 208.1, 64.3, 39.8, 38.5, 35.9, 33.6, 26.6, 20.9, 18.9.
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Spiro[5.5]undecane-1,7-dione (2e)
White solid; yield: 28.4 mg (79%).
1H NMR (400 MHz, CDCl3): δ = 2.55–2.38 (m, 6 H), 1.95–1.87 (m, 2 H), 1.82–1.70 (m, 6 H), 1.53–1.46 (m, 2 H).
13C NMR (101 MHz, CDCl3): δ = 211.0, 64.5, 40.8, 36.2, 27.7, 21.2.
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Spiro[5.6]dodecane-1,7-dione (2f)
White solid; yield: 17.8 mg (46%).
1H NMR (400 MHz, CDCl3): δ = 2.37 (t, J = 7.2 Hz, 2 H), 2.11–2.03 (m, 4 H), 1.92 (t, J = 7.5 Hz, 2 H), 1.72–1.60 (m, 6 H), 1.40–1.33 (m, 4 H).
13C NMR (101 MHz, CDCl3): δ = 212.6, 211.1, 66.4, 41.2, 41.0, 35.7, 32.9, 30.3, 27.0, 26.6, 24.8, 21.7.
HRMS (ESI): m/z calcd for C12H18O2 [M + H]+: 195.1380; found: 195.1376.
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Spiro[4.6]undecane-1,6-dione (2g)
Yellow liquid; yield: 19.8 mg (55%).
1H NMR (400 MHz, CDCl3): δ = 2.87 (td, J = 11.6, 2.6 Hz, 1 H), 2.70–2.63 (m, 1 H), 2.43–2.36 (m, 1 H), 2.34–2.20 (m, 2 H), 2.12–1.98 (m, 2 H), 1.91–1.74 (m, 4 H), 1.72–1.65 (m, 2 H), 1.58–1.42 (m, 2 H), 1.27–1.23 (m, 1 H).
13C NMR (101 MHz, CDCl3): δ = 216.3, 210.5, 67.8, 41.8, 38.4, 34.0, 33.5, 30.4, 26.3, 25.5, 19.2.
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Spiro[5.6]dodecane-1,7-dione (2h)
Yellow liquid; yield: 17.8 mg (46%).
1H NMR (400 MHz, CDCl3): δ = 2.59–2.42 (m, 4 H), 2.38–2.32 (m, 1 H), 2.28–2.23 (m, 1 H), 1.93–1.88 (m, 1 H), 1.78–1.52 (m, 11 H).
13C NMR (101 MHz, CDCl3): δ = 212.5, 211.0, 66.4, 41.2, 41.0, 35.7, 32.8, 30.2, 27.0, 26.6, 24.8, 21.7.
HRMS (ESI): m/z calcd for C12H18O2 [M + H]+: 195.1380; found: 195.1376.
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Spiro[6.6]tridecane-1,8-dione (2i)
White solid; yield: 20.8 mg (50%).
1H NMR (400 MHz, CDCl3): δ = 2.65 (td, J = 11.2, 2.6 Hz, 2 H), 2.39 (dd, J = 14.8, 10.6 Hz, 2 H), 2.34–2.28 (m, 2 H), 1.83–1.68 (m, 6 H), 1.61 (dd, J = 14.9, 8.9 Hz, 2 H), 1.55–1.40 (m, 4 H), 1.27–1.18 (m, 2 H).
13C NMR (101 MHz, CDCl3): δ = 210.8, 71.1, 40.9, 31.4, 30.3, 26.6, 24.2.
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Spiro[cyclopentane-1,2′-indene]-1′,2(3′H)-dione (2j)
White solid; yield: 26.0 mg (65%).
1H NMR (400 MHz, CDCl3): δ = 7.72 (d, J = 7.7 Hz, 1 H), 7.61 (td, J = 7.5, 1.2 Hz, 1 H), 7.48 (d, J = 7.7 Hz, 1 H), 7.39 (t, J = 7.4 Hz, 1 H), 3.51 (d, J = 17.0 Hz, 1 H), 2.94 (d, J = 17.0 Hz, 1 H), 2.64–2.55 (m, 2 H), 2.49–2.34 (m, 2 H), 2.12–2.00 (m, 2 H).
13C NMR (101 MHz, CDCl3): δ = 215.8, 203.8, 153.5, 135.3, 135.1, 127.8, 126.2, 124.5, 64.8, 38.0, 37.9, 34.7, 19.6.
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6′-Methylspiro[cyclopentane-1,2′-indene]-1′,2(3′H)-dione (2k)
White solid; yield: 27.0 mg (63%).
1H NMR (400 MHz, CDCl3): δ = 7.50 (s, 1 H), 7.42 (dd, J = 7.9, 1.7 Hz, 1 H), 7.35 (d, J = 7.8 Hz, 1 H), 3.44 (d, J = 16.8 Hz, 1 H), 2.87 (d, J = 16.8 Hz, 1 H), 2.60–2.52 (m, 2 H), 2.47–2.32 (m, 5 H), 2.10–1.99 (m, 2 H).
13C NMR (101 MHz, CDCl3): δ = 216.0, 203.9, 150.8, 137.7, 136.4, 135.4, 125.8, 124.4, 65.2, 38.0, 37.6, 34.7, 21.0, 19.6.
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5′-Methoxyspiro[cyclopentane-1,2′-indene]-1′,2(3′H)-dione (2l)
White solid; yield: 26.7 mg (58%).
1H NMR (400 MHz, CDCl3): δ = 7.65–7.63 (m, 1 H), 6.92–6.90 (m, 2 H), 3.88 (s, 3 H), 3.44 (d, J = 17.0 Hz, 1 H), 2.87 (d, J = 17.0 Hz, 1 H), 2.63–2.53 (m, 2 H), 2.49–2.31 (m, 2 H), 2.10–1.97 (m, 2 H).
13C NMR (101 MHz, CDCl3): δ = 216.3, 201.8, 165.6, 156.4, 128.3, 126.1, 115.9, 109.3, 64.9, 55.7, 37.9, 37.8, 34.6, 19.5.
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5′-Chlorospiro[cyclopentane-1,2′-indene]-1′,2(3′H)-dione (2m)
White solid; yield: 32.3 mg (69%).
1H NMR (400 MHz, CDCl3): δ = 7.64 (d, J = 8.2 Hz, 1 H), 7.48 (d, J = 1.6 Hz, 1 H), 7.38–7.35 (m, 1 H), 3.47 (d, J = 17.2 Hz, 1 H), 2.91 (d, J = 17.2 Hz, 1 H), 2.63–2.54 (m, 2 H), 2.49–2.35 (m, 2 H), 2.10–2.01 (m, 2 H).
13C NMR (101 MHz, CDCl3): δ = 215.3, 202.3, 154.9, 141.9, 133.8, 128.7, 126.5, 125.6, 65.1, 37.9, 37.5, 34.6, 19.6.
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2,2′-Spirobi[indene]-1,1′(3H,3′H)-dione (2n)
White solid; yield: 37.2 mg (75%).
1H NMR (400 MHz, CDCl3): δ = 7.77 (d, J = 7.7 Hz, 2 H), 7.66 (t, J = 7.5 Hz, 2 H), 7.57 (d, J = 7.8 Hz, 2 H), 7.42 (t, J = 7.5 Hz, 2 H), 3.74 (d, J = 17.0 Hz, 2 H), 3.21 (d, J = 17.0 Hz, 2 H).
13C NMR (101 MHz, CDCl3): δ = 202.7, 153.9, 135.5, 135.3, 127.9, 126.4, 125.0, 65.4, 38.2.
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6-Methyl-2,2′-spirobi[indene]-1,1′(3H,3′H)-dione (2o)
White solid; yield: 37.7 mg (72%).
1H NMR (400 MHz, CDCl3): δ = 7.76 (d, J = 7.7 Hz, 1 H), 7.66 (t, J = 7.4 Hz, 1 H), 7.57–7.56 (m, 2 H), 7.50–7.40 (m, 3 H), 3.70 (dd, J = 21.5, 16.9 Hz, 2 H), 3.17 (t, J = 17.3 Hz, 2 H), 2.42 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 202.9, 202.8, 153.9, 151.3, 137.9, 136.6, 135.7, 135.6, 135.3, 127.8, 126.4, 126.1, 124.9, 124.8, 65.8, 38.1, 37.8, 21.1.
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5-Fluoro-2,2′-spirobi[indene]-1,1′(3H,3′H)-dione (2p)
White solid; yield: 40.0 mg (79%).
1H NMR (400 MHz, CDCl3): δ = 7.76 (d, J = 7.1 Hz, 2 H), 7.66 (t, J = 7.5 Hz, 1 H), 7.57 (d, J = 7.7 Hz, 1 H), 7.42 (t, J = 7.5 Hz, 1 H), 7.24–7.22 (m, 1 H), 7.12 (t, J = 8.8 Hz, 1 H), 3.71 (dd, J = 17.1, 11.8 Hz, 2 H), 3.19 (dd, J = 17.2, 5.5 Hz, 2 H).
13C NMR (101 MHz, CDCl3): δ = 202.4, 200.8, 168.8, 166.2, 156.8, 156.7, 153.8, 135.5, 135.2, 131.8, 131.8, 127.9, 127.2, 127.1, 126.4, 125.0, 116.4, 116.1, 113.3, 113.1, 65.6, 37.9, 37.8, 37.7.
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1,3-Diketones 5a–5x; General Procedure
α-Substituted ketone 3 (0.2 mmol, 1.0 equiv), carboxylic acid 4 (0.2 mmol, 1.0 equiv), P2O5 (0.4 mmol, 2.0 equiv), and Tf2O (0.02 mmol, 0.1 equiv) were dissolved in DCM (2.0 mL) at room temperature and the reaction mixture was stirred at that same temperature until complete consumption of α-substituted ketone as detected by TLC. The solution was then quenched with saturated NaHCO3 and extracted with DCM (3 × 5 mL). The combined organic layer was washed with brine (20 mL), dried over anhydrous Na2SO4, and evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel to afford the 1,3-diketone 5a–5x.
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2-Benzoyl-2-methyl-2,3-dihydro-1H-inden-1-one (5a)
White solid; yield: 25.0 mg (50%).
1H NMR (400 MHz, CDCl3): δ = 7.90 (d, J = 7.7 Hz, 1 H), 7.70 (td, J = 7.5, 1.3 Hz, 1 H), 7.59–7.56 (m, 2 H), 7.54–7.49 (m, 2 H), 7.46–7.43 (m, 1 H), 7.31–7.27 (m, 2 H), 3.76 (d, J = 17.6 Hz, 1 H), 3.10 (d, J = 17.6 Hz, 1 H), 1.59 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 204.9, 198.4, 151.8, 135.4, 135.2, 134.9, 132.7, 128.5, 128.2, 128.2, 127.1, 125.2, 61.7, 40.7, 22.9.
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2-Methyl-2-(2-phenylacetyl)-2,3-dihydro-1H-inden-1-one (5b)
White solid; yield: 33.3 mg (63%).
1H NMR (400 MHz, CDCl3): δ = 7.77 (d, J = 7.7 Hz, 1 H), 7.62 (td, J = 7.5, 1.2 Hz, 1 H), 7.48 (d, J = 7.7 Hz, 1 H), 7.40 (t, J = 7.5 Hz, 1 H), 7.28–7.18 (m, 3 H), 7.13–7.11 (m, 2 H), 3.99–3.84 (m, 3 H), 2.86 (d, J = 17.5 Hz, 1 H), 1.60 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 204.1, 203.9, 152.9, 135.5, 134.8, 133.9, 129.6, 128.3, 127.8, 126.8, 126.5, 124.7, 63.9, 44.7, 37.8, 21.6.
HRMS (ESI): m/z calcd for C18H16O2 [M + H]+: 265.1220; found: 265.1223.
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2-Methyl-2-(3-phenylpropanoyl)-2,3-dihydro-1H-inden-1-one (5c)
Yellow viscous liquid; yield: 41.7 mg (75%).
1H NMR (400 MHz, CDCl3): δ = 7.83 (d, J = 7.7 Hz, 1 H), 7.70 (td, J = 7.5, 1.2 Hz, 1 H), 7.55 (d, J = 7.7 Hz, 1 H), 7.47 (t, J = 7.5 Hz, 1 H), 7.35–7.27 (m, 2 H), 7.27–7.22 (m, 3 H), 3.80 (d, J = 17.4 Hz, 1 H), 3.07–2.86 (m, 5 H), 1.59 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 205.7, 204.2, 152.9, 140.9, 135.4, 134.8, 128.4, 128.3, 127.8, 126.5, 126.0, 124.7, 63.6, 39.9, 37.7, 29.8, 21.2.
HRMS (ESI): m/z calcd for C19H18O2 [M + H]+: 279.1380; found: 279.1373.
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2-Cinnamoyl-2-methyl-2,3-dihydro-1H-inden-1-one (5d)
White solid; yield: 36.4 mg (66%).
1H NMR (400 MHz, CDCl3): δ = 7.70 (d, J = 7.7 Hz, 1 H), 7.62–7.54 (m, 2 H), 7.45–7.42 (m, 3 H), 7.35–7.31 (m, 1 H), 7.29–7.25 (m, 3 H), 7.06 (d, J = 15.6 Hz, 1 H), 3.93 (d, J = 17.5 Hz, 1 H), 2.84 (d, J = 17.5 Hz, 1 H), 1.54 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 204.4, 194.9, 152.9, 144.3, 135.4, 135.2, 134.4, 130.6, 128.8, 128.6, 127.8, 126.6, 124.7, 121.0, 62.9, 37.5, 21.6.
HRMS (ESI): m/z calcd for C19H16O2 [M + H]+: 277.1223; found: 277.1220.
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2-(2-((3r,5r,7r)-Adamantan-1-yl)acetyl)-2-methyl-2,3-dihydro-1H-inden-1-one (5e)
White solid; yield: 41.2 mg (64%).
1H NMR (400 MHz, CDCl3): δ = 7.75 (d, J = 7.6 Hz, 1 H), 7.63 (td, J = 7.5, 1.3 Hz, 1 H), 7.49 (dt, J = 7.7, 1.0 Hz, 1 H), 7.42–7.37 (m, 1 H), 3.77 (d, J = 17.5 Hz, 1 H), 2.80 (d, J = 17.4 Hz, 1 H), 2.38–2.21 (m, 2 H), 1.91–1.88 (m, 3 H), 1.67–1.53 (m, 12 H), 1.48 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 205.4, 204.4, 152.9, 135.3, 135.2, 127.7, 126.5, 124.6, 64.6, 50.4, 41.9, 37.7, 36.7, 33.0, 28.5, 21.1.
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2-Methyl-2-(2-(naphthalen-1-yl)acetyl)-2,3-dihydro-1H-inden-1-one (5f)
White solid; yield: 42.1 mg (67%).
1H NMR (400 MHz, CDCl3): δ = 7.80–7.73 (m, 4 H), 7.63–7.57 (m, 2 H), 7.47–7.38 (m, 4 H), 7.26 (dd, J = 8.5, 1.8 Hz, 1 H), 4.18–4.01 (m, 2 H), 3.90 (d, J = 17.5 Hz, 1 H), 2.87 (d, J = 17.5 Hz, 1 H), 1.64 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 204.1, 204.1, 152.8, 135.5, 134.7, 133.3, 132.2, 131.4, 128.3, 127.9, 127.8, 127.7, 127.5, 127.5, 126.5, 125.9, 125.6, 124.7, 63.9, 44.9, 37.7, 21.6.
#
2-(2-(2,3-Dihydrobenzofuran-5-yl)acetyl)-2-methyl-2,3-dihydro-1H-inden-1-one (5g)
Yellow viscous liquid; yield: 29.4 mg (48%).
1H NMR (400 MHz, CDCl3): δ = 7.77 (dt, J = 7.7, 0.9 Hz, 1 H), 7.63 (td, J = 7.5, 1.2 Hz, 1 H), 7.48 (dt, J = 7.7, 1.0 Hz, 1 H), 7.43–7.39 (m, 1 H), 6.95 (d, J = 1.7 Hz, 1 H), 6.82 (dd, J = 8.2, 1.9 Hz, 1 H), 6.66 (d, J = 8.1 Hz, 1 H), 4.52 (t, J = 8.7 Hz, 2 H), 3.93–3.74 (m, 3 H), 3.14 (t, J = 8.7 Hz, 2 H), 2.86 (d, J = 17.5 Hz, 1 H), 1.59 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 204.7, 204.2, 158.9, 152.9, 135.5, 134.8, 129.2, 127.8, 127.2, 126.5, 126.2, 125.5, 124.7, 109.0, 71.2, 63.8, 44.2, 37.9, 29.6, 21.6.
#
2-Methyl-2-(2-phenylacetyl)cyclopentan-1-one (5h)
Yellow liquid; yield: 16.4 mg (38%).
1H NMR (400 MHz, CDCl3): δ = 7.31–7.23 (m, 3 H), 7.14–7.12 (m, 2 H), 3.94–3.78 (m, 2 H), 2.71–2.64 (m, 1 H), 2.29–2.23 (m, 2 H), 1.90–1.83 (m, 2 H), 1.71–1.64 (m, 1 H), 1.39 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 216.9, 204.8, 133.7, 129.7, 128.5, 126.9, 63.9, 44.7, 38.1, 34.1, 20.6, 19.2.
HRMS (ESI): m/z calcd for C14H16O2 [M + Na]+: 239.1041; found: 239.1043.
#
2-Methyl-2-(3-phenylpropanoyl)cyclopentan-1-one (5i)
Yellow liquid; yield: 24.8 mg (54%).
1H NMR (400 MHz, CDCl3): δ = 7.29–7.25 (m, 2 H), 7.20–7.15 (m, 3 H), 2.92–2.78 (m, 4 H), 2.61–2.55 (m, 1 H), 2.27–2.23 (m, 2 H), 1.90–1.83 (m, 2 H), 1.67–1.58 (m, 1 H), 1.28 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 216.9, 206.8, 140.9, 128.4, 128.4, 126.1, 63.6, 39.9, 38.0, 34.0, 29.8, 20.3, 19.2.
#
2-Methyl-2-(3-(p-tolyl)propanoyl)cyclopentan-1-one (5j)
Yellow liquid; yield: 27.3 mg (56%).
1H NMR (400 MHz, CDCl3): δ = 7.10–7.05 (m, 4 H), 2.89–2.79 (m, 4 H), 2.63–2.56 (m, 1 H), 2.32 (s, 3 H), 2.29–2.25 (m, 2 H), 1.92–1.85 (m, 2 H), 1.69–1.62 (m, 1 H), 1.29 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 216.9, 206.9, 137.8, 135.5, 129.1, 128.2, 63.6, 40.0, 38.0, 34.0, 29.3, 21.0, 20.2, 19.2.
HRMS (ESI): m/z calcd for C16H20O2 [M + Na]+: 267.1356; found: 267.1354.
#
2-(3-(4-Methoxyphenyl)propanoyl)-2-methylcyclopentan-1-one (5k)
Yellow liquid; yield: 26.5 mg (51%).
1H NMR (400 MHz, CDCl3): δ = 7.10–7.07 (m, 2 H), 6.83–6.80 (m, 2 H), 3.78 (s, 3 H), 2.89–2.76 (m, 4 H), 2.61–2.55 (m, 1 H), 2.26 (t, J = 8.0 Hz, 2 H), 1.91–1.83 (m, 2 H), 1.67–1.60 (m, 1 H), 1.28 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 216.9, 206.9, 157.9, 133.0, 129.3, 113.8, 63.6, 55.2, 40.1, 38.0, 34.0, 28.9, 20.2, 19.2.
HRMS (ESI): m/z calcd for C16H20O3 [M + Na]+: 283.1305; found: 283.1303.
#
2-(3-(4-Fluorophenyl)propanoyl)-2-methylcyclopentan-1-one (5l)
Yellow liquid; yield: 28.3 mg (57%).
1H NMR (400 MHz, CDCl3): δ = 7.14–7.09 (m, 2 H), 6.97–6.93 (m, 2 H), 2.91–2.76 (m, 4 H), 2.61–2.54 (m, 1 H), 2.26 (td, J = 7.8, 2.6 Hz, 2 H), 1.91–1.84 (m, 2 H), 1.67–1.60 (m, 1 H), 1.28 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 216.9, 206.6, 162.5, 160.1, 136.5, 136.5, 129.8, 129.7, 115.2, 115.0, 63.6, 39.8, 38.0, 33.9, 28.9, 20.3, 19.2.
19F NMR (376 MHz, CDCl3): δ = –117.0.
HRMS (ESI): m/z calcd for C15H17FO2 [M + Na]+: 271.1105; found: 271.1101.
#
2-Ethyl-2-(3-phenylpropanoyl)cyclopentan-1-on (5m)
Colorless liquid; yield: 23.9 mg (49%).
1H NMR (400 MHz, CDCl3): δ = 7.28–7.24 (m, 2 H), 7.19–7.15 (m, 3 H), 3.02–2.95 (m, 1 H), 2.86–2.73 (m, 3 H), 2.68–2.62 (m, 1 H), 2.17 (dd, J = 8.8, 6.8 Hz, 2 H), 2.03–1.94 (m, 1 H), 1.89–1.81 (m, 1 H), 1.79–1.71 (m, 1 H), 1.67–1.58 (m, 2 H), 0.74 (t, J = 7.5 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 216.2, 205.5, 140.9, 128.4, 128.4, 126.0, 69.4, 39.4, 38.6, 30.1, 29.8, 27.9, 19.3, 9.2.
HRMS (ESI): m/z calcd for C16H20O2 [M + H]+: 245.1536; found: 245.1530.
#
2-Methyl-2-(2-phenylacetyl)-3,4-dihydronaphthalen-1(2H)-one (5n)
White solid; yield: 26.1 mg (47%).
1H NMR (400 MHz, CDCl3): δ = 8.03 (dd, J = 7.9, 1.4 Hz, 1 H), 7.47 (td, J = 7.5, 1.5 Hz, 1 H), 7.32–7.28 (m, 1 H), 7.25–7.18 (m, 3 H), 7.16–7.12 (m, 1 H), 7.10–7.07 (m, 2 H), 2.93–2.90 (m, 1 H), 2.85–2.81 (m, 2 H), 2.62–2.54 (m, 2 H), 1.94–1.87 (m, 1 H), 1.37 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 205.9, 198.3, 143.5, 133.8, 133.6, 131.8, 129.6, 128.8, 128.3, 127.8, 126.8, 126.7, 60.1, 45.2, 32.4, 25.7, 21.0.
#
2-Methyl-2-(3-phenylpropanoyl)-3,4-dihydronaphthalen-1(2H)-one (5o)
White solid; yield: 31.0 mg (53%).
1H NMR (400 MHz, CDCl3): δ = 8.03 (dd, J = 7.9, 1.5 Hz, 1 H), 7.48 (td, J = 7.5, 1.5 Hz, 1 H), 7.31 (td, J = 7.6, 1.2 Hz, 1 H), 7.24–7.18 (m, 3 H), 7.14–7.08 (m, 3 H), 2.95–2.89 (m, 3 H), 2.85–2.81 (m, 2 H), 2.62–2.54 (m, 2 H), 1.94–1.87 (m, 1 H), 1.37 (s, 3 H).
13C NMR (101 MHz, CDCl3): δ = 207.9, 198.4, 143.5, 140.8, 133.8, 131.7, 128.9, 128.3, 128.3, 127.8, 126.8, 126.0, 59.8, 40.5, 32.4, 29.7, 25.7, 20.8.
HRMS (ESI): m/z calcd for C20H20O2 [M + H]+: 293.1536; found: 293.1528.
#
3,3-Dimethyl-6-phenylhexane-2,4-dione (5p)
Yellow liquid; yield: 24.9 mg (57%).
1H NMR (400 MHz, CDCl3): δ = 7.27–7.23 (m, 2 H), 7.18–7.13 (m, 3 H), 2.88 (t, J = 7.4 Hz, 2 H), 2.73–2.69 (m, 2 H), 1.94 (s, 3 H), 1.28 (s, 6 H).
13C NMR (101 MHz, CDCl3): δ = 208.7, 207.6, 140.8, 128.4, 128.4, 126.2, 62.5, 40.2, 29.8, 26.0, 21.1.
HRMS (ESI): m/z calcd for C14H18O2 [M + Na]+: 241.1199; found: 241.1196.
#
3,3-Dimethyl-6-(p-tolyl)hexane-2,4-dione (5q)
Yellow liquid; yield: 26.5 mg (57%).
1H NMR (400 MHz, CDCl3): δ = 7.10–7.05 (m, 4 H), 2.86 (t, J = 7.4 Hz, 2 H), 2.72–2.69 (m, 2 H), 2.31 (s, 3 H), 1.98 (s, 3 H), 1.30 (s, 6 H).
13C NMR (101 MHz, CDCl3): δ = 208.8, 207.7, 137.7, 135.6, 129.1, 128.3, 62.5, 40.3, 29.3, 26.0, 21.0, 20.9.
HRMS (ESI): m/z calcd for C15H20O2 [M + Na]+: 255.1356; found: 255.1354.
#
6-(4-Methoxyphenyl)-3,3-dimethylhexane-2,4-dione (5r)
Yellow liquid; yield: 16.9 mg (34%).
1H NMR (400 MHz, CDCl3): δ = 7.08 (d, J = 8.6 Hz, 2 H), 6.81 (d, J = 8.6 Hz, 2 H), 3.78 (s, 3 H), 2.84 (t, J = 7.3 Hz, 2 H), 2.69 (t, J = 7.0 Hz, 2 H), 1.96 (s, 3 H), 1.29 (s, 6 H).
13C NMR (101 MHz, CDCl3): δ = 208.8, 207.7, 158.0, 132.8, 129.4, 113.8, 62.5, 55.2, 40.4, 28.9, 26.1, 21.0.
HRMS (ESI): m/z calcd for C15H20O3 [M + Na]+: 271.1305; found: 271.1303.
#
6-(4-Fluorophenyl)-3,3-dimethylhexane-2,4-dione (5s)
Yellow liquid; yield: 17.9 mg (38%).
1H NMR (400 MHz, CDCl3): δ = 7.13–7.10 (m, 2 H), 6.96–6.92 (m, 2 H), 2.86 (t, J = 7.2 Hz, 2 H), 2.69 (t, J = 7.1 Hz, 2 H), 1.95 (s, 3 H), 1.29 (s, 6 H).
13C NMR (101 MHz, CDCl3): δ = 208.5, 207.7, 162.5, 160.1, 136.4, 136.4, 129.9, 129.8, 115.3, 115.1, 62.5, 40.2, 28.9, 26.0, 21.0.
19F NMR (376 MHz, CDCl3): δ = –117.1.
HRMS (ESI): m/z calcd for C14H17FO2 [M + Na]+: 259.1105; found: 259.1104.
#
3,3-Dimethyl-6-phenylheptane-2,4-dione (5t)
Yellow liquid; yield: 21.8 mg (47%).
1H NMR (400 MHz, CDCl3): δ = 7.29–7.25 (m, 2 H), 7.20–7.15 (m, 3 H), 3.40–3.34 (m, 1 H), 2.77–2.58 (m, 2 H), 1.85 (s, 3 H), 1.27–1.22 (m, 9 H).
13C NMR (101 MHz, CDCl3): δ = 208.0, 207.5, 145.9, 128.4, 126.9, 126.3, 62.7, 46.9, 34.7, 26.0, 21.6, 20.9, 20.8.
HRMS (ESI): m/z calcd for C15H20O2 [M + Na]+: 255.1356; found: 255.1354.
#
3-Ethyl-3-methyl-1-phenylpentane-2,4-dione (5u)
Colorless liquid; yield: 20.9 mg (48%).
1H NMR (400 MHz, CDCl3): δ = 7.33–7.23 (m, 3 H), 7.17–7.15 (m, 2 H), 3.70 (d, J = 4.8 Hz, 2 H), 2.05 (s, 3 H), 2.02–1.92 (m, 2 H), 1.36 (s, 3 H), 0.81 (t, J = 7.5 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 207.5, 206.6, 133.6, 129.6, 128.5, 127.0, 67.2, 45.2, 27.1, 26.7, 17.4, 8.5.
HRMS (ESI): m/z calcd for C14H18O2 [M + Na]+: 241.1199; found: 241.1195.
#
3-Ethyl-3-methyl-6-phenylhexane-2,4-dione (5v)
Colorless liquid; yield: 27.8 mg (60%).
1H NMR (400 MHz, CDCl3): δ = 7.28–7.25 (m, 2 H), 7.20–7.15 (m, 3 H), 2.88 (t, J = 7.4 Hz, 2 H), 2.76–2.62 (m, 2 H), 1.92 (s, 3 H), 1.87 (q, J = 7.5 Hz, 2 H), 1.26 (s, 3 H), 0.75 (t, J = 7.5 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 208.4, 207.4, 140.8, 128.4, 128.4, 126.1, 66.9, 40.6, 29.7, 26.9, 26.4, 17.1, 8.4.
HRMS (ESI): m/z calcd for C15H20O2 [M + H]+: 233.1536; found: 233.1531.
#
4,4-dimethyl-1-phenylheptane-3,5-dione (5w)
Colorless liquid; yield: 23.7 mg (51%).
1H NMR (400 MHz, CDCl3): δ = 7.28–7.24 (m, 2 H), 7.20–7.14 (m, 3 H), 2.88 (t, J = 7.4 Hz, 2 H), 2.72–2.68 (m, 2 H), 2.25 (q, J = 7.2 Hz, 2 H), 1.30 (s, 6 H), 0.94 (t, J = 7.2 Hz, 3 H).
13C NMR (101 MHz, CDCl3): δ = 210.4, 208.8, 140.8, 128.5, 128.4, 126.2, 62.3, 40.3, 31.6, 29.8, 21.2, 7.9.
HRMS (ESI): m/z calcd for C15H20O2 [M + H]+: 233.1536; found: 233.1531.
#
4,4,6-trimethyl-1-phenylheptane-3,5-dione (5x)
Colorless liquid; yield: 23.6 mg (48%).
1H NMR (400 MHz, CDCl3): δ = 7.29–7.24 (m, 2 H), 7.20–7.15 (m, 3 H), 2.90–2.86 (m, 2 H), 2.84–2.79 (m, 1 H), 2.74–2.70 (m, 2 H), 1.32 (s, 6 H), 1.00 (d, J = 6.7 Hz, 6 H).
13C NMR (101 MHz, CDCl3): δ = 214.4, 208.9, 140.9, 128.5, 128.4, 126.2, 62.8, 40.5, 36.3, 29.9, 21.2, 20.0.
#
#
Conflict of Interest
The authors declare no conflict of interest.
Supporting Information
- Supporting information for this article is available online at https://doi-org.accesdistant.sorbonne-universite.fr/10.1055/s-0043-1775472.
- Supporting Information
- CIF File
-
References
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Corresponding Authors
Publication History
Received: 24 February 2025
Accepted after revision: 26 March 2025
Article published online:
24 April 2025
© 2025. Thieme. All rights reserved
Georg Thieme Verlag KG
Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
-
References
- 1a Claisen L, Claparède A. Ber. Dtsch. Chem. Ges. 1881; 14: 349
- 1b Heath RJ, Rock CO. Nat. Prod. Rep. 2002; 19: 581
- 1c Misaki T, Nagase R, Matsumoto K, Tanabe Y. J. Am. Chem. Soc. 2005; 127: 2854
- 1d Kamijo S, Dudley GB. Org. Lett. 2006; 8: 175
- 1e Tamagaki H, Nawate Y, Nagase R, Tanabe Y. Chem. Commun. 2010; 46: 5930
- 1f Horta JE. J. Chem. Educ. 2011; 88: 1014
- 1g Chen J, Xu M, Yu S, Xia Y, Lee S. Org. Lett. 2020; 22: 2287
- 2 Esteb JJ, Stockton MB. J. Chem. Educ. 2003; 80: 1446
- 3a Vollhardt KP. C, Schore NE. Organic Chemistry, 3rd ed. 1999; 1039
- 3b Smith MB, March J. Advanced Organic Chemistry, 5th ed. 2001; 569
- 3c Clayden J, Greeves N, Warren S, Wothers P. Organic Chemistry . Oxford University Press; Oxford: 2001: 726
- 3d Iida A, Takai K, Okabayashi T, Misaki T, Tanabe Y. Chem. Commun. 2005; 3171
- 4a Nishimura T, Sunagawa M, Okajima T, Fukazawa Y. Tetrahedron Lett. 1997; 38: 7063
- 4b Jones DM, Lisboa MP, Kamijo S, Dudley GB. J. Org. Chem. 2010; 75: 3260
- 5a Yoshida Y, Hayashi R, Sumihara H, Tanabe Y. Tetrahedron Lett. 1997; 38: 8727
- 5b Yoshida Y, Matsumoto N, Hamasaki R, Tanabe Y. Tetrahedron Lett. 1999; 40: 4227
- 5c Honda Y, Katayama S, Kojima M, Suzuki T, Izawa K. Org. Lett. 2002; 4: 447
- 5d Mermerian AH, Fu GC. J. Am. Chem. Soc. 2005; 127: 5604
- 5e Iida A, Nakazawa S, Okabayashi T, Horii A, Misaki T, Tanabe Y. Org. Lett. 2006; 8: 5215
- 5f Iida A, Osada J, Nagase R, Misaki T, Tanabe Y. Org. Lett. 2007; 9: 1859
- 6a Fleming I, Goldhill J, Paterson I. Tetrahedron Lett. 1979; 20: 3205
- 6b Katritzky AR, Pastor A. J. Org. Chem. 2000; 65: 3679
- 6c Mermerian AH, Fu GC. J. Am. Chem. Soc. 2003; 125: 4050
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- 10 CCDC 2156569 (5d) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.
