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1-(((6-(Methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic Acid

by
Evgenii S. Gorlov
1,
Diana V. Shuingalieva
1,2,3,
Alexey I. Ilovaisky
1,3,
Vera A. Vil’
1,3,* and
Alexander O. Terent’ev
1,3,*
1
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, Moscow 119991, Russia
2
Faculty of Engineering Chemical Technology, D. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Square, Moscow 125047, Russia
3
All-Russian Research Institute for Phytopathology, B. Vyazyomy, Moscow 143050, Russia
*
Authors to whom correspondence should be addressed.
Molbank 2023, 2023(2), M1651; https://doi.org/10.3390/M1651
Submission received: 4 May 2023 / Revised: 17 May 2023 / Accepted: 22 May 2023 / Published: 24 May 2023
(This article belongs to the Section Organic Synthesis and Biosynthesis)
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Abstract

:
Here, we first report the 2′-acyloxy-1,3-dicarbonyl compound construction in a three-component oxidative reaction of alkyl ketene dimer with cyclic diacyl peroxide and trimethyl orthoformate. The discovered synthesis allows us to form 2′-functionalized 1,3-dicarbonyl compounds instead of the common 2-functionalized moiety. The reaction between 4-butylidene-3-propyloxetan-2-one and cyclopropyl malonoyl peroxide proceeds in the presence of trifluoroacetic acid and trimethyl orthoformate at 120 °C for 1 h. The synthesized compound was characterized by NMR spectroscopy, mass spectrometry, and IR spectroscopy.

1. Introduction

Alkyl ketene dimers were first synthesized in 1901 [1] and their reactivity is mostly determined by a strained oxetan-2-one ring, which readily reacts with various nucleophiles [2,3,4,5,6] (Scheme 1). Also, alkyl ketene dimers can be regarded as acyl enolates. However, there are only scattered reports on metal-catalyzed oxidation of diketene [7,8,9], and there is only one example of metal-free oxidation by ozone [10,11]. So, further investigation of oxidative transformations of ketene dimers would be desirable. Our idea is that such a transformation is possible using cyclic diacyl peroxides as oxidants (Scheme 1).
Cyclic diacyl peroxides were first synthesized in the 1950s [12,13], and their chemical properties are still being intensively studied [14,15]. A search for new interesting structures based on cyclic diacyl peroxides continues as well, and recently a doubled cyclic diacyl peroxide has been reported that may be useful for polymer chemistry [16]. Cyclic diacyl peroxides are utilized in dihydroxylation, dioxygenation [17,18,19,20,21,22,23], and oxyamination [24] of alkenes. Oxyfunctionalization of arenes [25,26,27,28,29,30,31] as well as arene dearomatization [32] were achieved using these peroxides. Oxidative acyloxylation of dicarbonyl compounds [33], heterocycles [34], and the derivatives of monocarbonyl compounds [35,36] also were developed. Recently, our group reported on the reaction of enol acetates with cyclic diacyl peroxides, which proceeds as a nucleophilic substitution of an oxygen atom (SN2@O) [37] and Ni-catalyzed C(sp3)-H acyloxylation [38,39] with such reagents. Here, we report the 2′-acyloxy-1,3-dicarbonyl compound construction in a three-component oxidative reaction of alkyl ketene dimer with cyclic diacyl peroxide and trimethyl orthoformate.

2. Results and Discussion

4-Butylidene-3-propyloxetan-2-one 1 and cyclopropyl malonoyl peroxide 2 were chosen to study the oxidation of alkyl ketene dimers with cyclic diacyl peroxides. Moreover, an important component of the reaction is a nucleophile, whose role is to intercept the supposed unstable intermediate. Since cyclic diacyl peroxide 2 can react with the nucleophile, the choice of nucleophile is not trivial. Alkyl ketene dimers, being acylating agents, are also labile to a nucleophilic attack. Thus, the nucleophile must be inert towards the peroxide and the alkyl ketene dimer, and it must be able to react with the intermediate at the same time.
Surprisingly, when trimethyl orthoformate was used as the nucleophile, and TFA as a source of protons, product 3 was obtained with the NMR yield of 43% (Scheme 2). The reaction was completed in 1 hour in a sealed vessel at 120 °C.
To our delight, there was no further oxidation of 3 by cyclopropyl malonoyl peroxide 2, despite the possibility of such a process, which was described in the literature [33]. Product 3 was isolated as a mixture of two diastereomers in a ratio of 50:50 using column chromatography. Interestingly, one of the diastereomers predominates right after the reaction, but during the work-up, the mixture is racemized, probably due to keto-enol tautomerism. The mixture of diastereomers 3 was characterized by NMR, IR spectroscopy, and mass spectrometry (Figures S5–S8, Supplementary Materials). The 1H NMR spectrum of compound 3 showed signals for two methyne protons at δ 5.35, 5.21 (both dd, 1H, C(O)CH(O)CH2) and δ 3.59 (dt, 1H, C(O)CHC(O)), signals of CH3O group at δ 3.75, 3.70 (both s, 3H), as well as three multiples related to CH2 and CH2CH3 protons at δ 1.98–1.69 (m, 8H), 1.40–1.23 (m, 4H), 0.97–0.88 (m, 6H). The 13C NMR spectra of compound 3 showed double sets of signals for most of the atoms. The analysis of the carbon resonances revealed the presence of two signals for C=O (δ 200.5, 199.8), signals for three ester fragments (δ 175.4; 170.3; 169.1, 168.9), two signals for one oxygenated tertiary carbon (δ 79.6, 79.0). Additionally, the close signals of sp3 tertiary carbon and OCH3 group were detected (δ 55.4, 54.8; 52.9, 52.7).
The plausible mechanism for the three-component oxidative reaction of alkyl ketene dimer with cyclic diacyl peroxide and trimethyl orthoformate was proposed based on the above-mentioned results and the data (Scheme 3) [20,21,22,23,24,25,26,27,33,34,35,36,37,38,39]. Initially, the nucleophilic attack of the C=C double bond of alkyl ketene dimer 1 to cyclic diacyl peroxide 2 leads to the formation of intermediate I. Then, it can be assumed that either a direct interaction of trimethyl orthoformate with intermediate I occurs, or methanol is generated in situ and then is added to intermediate I to form the final product 3.

3. Materials and Methods

3.1. General Information

Caution: Peroxides are high-energy compounds. All reactions using these substances should be conducted within a fume hood and behind a safety shield. These procedures should be carried out by knowledgeable laboratory workers.
NMR spectra were recorded on commercial instruments (300.13 MHz for 1H, 75.48 MHz for 13C) in CDCl3. The IR spectrum was recorded with a Bruker (Moscow, Russia) “Alpha-T” instrument. High-resolution mass spectrum (HRMS) was measured using electrospray ionization (ESI-TOF) [40]. The measurement was carried out in a positive ion mode (interface capillary voltage—4500 V); mass range from m/z 50 to m/z 1600 Da; and external/internal calibration was done with an electrospray calibrant solution. A syringe injection was used for solutions in CH3CN (flow rate 3 μL/min). Nitrogen was applied as a dry gas; the interface temperature was set at 180 °C. The TLC analysis was carried out on standard silica gel chromatography plates. Silica gel was calcined in a vacuum oven at 200 °C for 2 h before use.

3.2. Synthesis of 4-Butylidene-3-propyloxetan-2-one (1)

Compound 1 was synthesized according to the modified literature method [41].
A solution of triethylamine (2.13 g, 21.0 mmol) in 10 mL of diethyl ether was added to a solution of valeroyl chloride (2.41 g, 20.0 mmol), whilst being stirred, in diethyl ether (10 mL) over 1 hour at 0 °C. The resulting solution was stirred for 24 h at room temperature. Then, the solution was filtered and a precipitate was washed with diethyl ether (2 × 20 mL). A filtrate was concentrated under reduced pressure using a rotary evaporator (15–20 mmHg, a water bath temperature ca. 20–25 °C). A residue was transferred on the top of chromatographic column and product 1 was isolated by column chromatography on SiO2 (see Section 3.1 General Information) (the gradient system PE:EtOAc = 40:1). Product 1 was obtained as a colorless liquid (0.91 g, 5.43 mmol, 54% yield).
1H NMR (300 MHz, CDCl3): δ 4.69 (t, J = 7.7 Hz, 1H), 3.94 (t, J = 7.2 Hz, 1H), 2.10 (q, J = 7.2 Hz, 2H), 1.76 (q, J = 7.7, 7.2 Hz, 2H), 1.55–1.37 (m, 4H), 0.96 (t, J = 6.9 Hz, 3H), 0.91 (t, J = 6.9 Hz, 3H).
13C NMR (75 MHz, CDCl3): δ 169.8, 145.9, 101.5, 53.7, 29.7, 26.8, 22.7, 19.9, 13.8, 13.7.
The data are fully consistent with those previously published [42].

3.3. Synthesis of Cyclopropyl Malonoyl Peroxide (2)

The cyclopropyl malonoyl peroxide (2) was synthesized according to the method in the literature [27]. The data are fully consistent with those previously published [27].
1H NMR (300 MHz, CDCl3): δ 2.09 (s, 4H).
13C NMR (76 MHz, CDCl3); δ 172.3, 23.8, 19.9.

3.4. Synthesis of 1-(((6-(Methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic acid (3)

Trifluoroacetic acid (114.0 mg, 1.0 mmol) was added to a mixture of 4-butylidene-3-propyloxetan-2-one (1) (168.0 mg, 1.0 mmol), cyclopropyl malonoyl peroxide (2) (179.0 mg, 1.4 mmol), and trimethyl orthoformate (530.0 mg, 5.0 mmol). The reaction mixture was stirred in a sealed vessel for 1 hour at 120 °C. Then, the mixture was diluted with diethyl ether (5 mL) and transferred to a flask to concentrate under reduced pressure using a rotary evaporator (15–20 mmHg, a water bath temperature ca. 40 °C). A residue was transferred on the top of chromatographic column and product 3 was isolated by column chromatography on SiO2 (the gradient system PE:EtOAc from 8:1 to 2:1 with 0.5 % AcOH). Product 3 was obtained as a colorless oil (124.0 mg, 0.38 mmol, 38% yield).
1H NMR (300 MHz, CDCl3): δ 5.35 (dd, J = 8.8, 3.7 Hz), 5.21 (dd, J = 8.5, 3.9 Hz) (total 1H), 3.79–3.70 (m, 3H), 3.59 (dt, J = 12.0, 7.5 Hz, 1H), 1.98–1.69 (m, 8H), 1.40–1.23 (m, 4H), 0.97–0.88 (m, 6H).
13C{1H} NMR (75 MHz, CDCl3): δ 200.5, 199.8, 175.4, 170.3, 169.1, 168.9, 79.6, 79.0, 55.4, 54.8, 52.9, 52.7, 31.8, 31.6, 31.1, 29.7, 25.41, 25.37, 23.3, 22.3, 22.0, 20.8, 20.6, 18.8, 18.6, 13.9, 13.7.
HRMS (ESI-TOF) m/z [M+Na]+. Calcd for [C16H24O7Na]+: 351.1414. Found: 351.1415.
IR (KBr), ν, cm−1: 3122 (COO-H), 2963 (C-H), 2876 (C-H), 1727 (C=O), 1437, 1381, 1332, 1269, 1240, 1194, 1159, 1048, 977, 865, 820, 737, 677, 519.

4. Conclusions

The 2′-acyloxy-1,3-dicarbonyl compound was obtained in a three-component oxidative reaction of alkyl ketene dimer with cyclic diacyl peroxide and trimethyl orthoformate in a 38% isolated yield. The reaction between 4-butylidene-3-propyloxetan-2-one and cyclopropyl malonoyl peroxide to form 1-(((6-(methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic acid proceeds in the presence of trifluoroacetic acid and trimethyl orthoformate at 120 °C for 1 h. The chemistry of ketene dimers has been extended by the use of cyclic diacyl peroxides.

Supplementary Materials

The following supporting information can be downloaded online: Figure S1. 1H NMR spectrum of 4-butylidene-3-propyloxetan-2-one (1); Figure S2. 13C NMR spectrum of 4-butylidene-3-propyloxetan-2-one (1); Figure S3. 1H NMR spectrum of cyclopropyl malonoyl peroxide (2); Figure S4. 13C NMR spectrum of cyclopropyl malonoyl peroxide (2); Figure S5. 1H NMR spectrum of 1-(((6-(methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic acid (3); Figure S6. 13C NMR spectrum of 1-(((6-(methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic acid (3); Figure S7. IR spectrum of 1-(((6-(methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic acid (3); Figure S8. HRMS spectrum of 1-(((6-(methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic acid (3).

Author Contributions

D.V.S. conducted the experiments and analyzed the data; E.S.G. designed the study and the experiments and analyzed the data; V.A.V. designed the study and wrote the manuscript; A.I.I. reviewed and edited the final manuscript to publish; A.O.T. supervised the progress of work and reviewed and edited the final manuscript to publish. All authors have read and agreed to the published version of the manuscript.

Funding

The study was supported by the Russian Science Foundation (Grant No 19-73-20190).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

High-resolution mass-spectrometry study was performed in the Department of Structural Studies of Zelinsky Institute of Organic Chemistry, Moscow.

Conflicts of Interest

The authors declare no conflict of interest.

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Molbank 2023 m1651 sch001 550
Scheme 1. The core fragment of alkyl ketene dimers and its reactivity.
Scheme 1. The core fragment of alkyl ketene dimers and its reactivity.
Molbank 2023 m1651 sch001
Molbank 2023 m1651 sch002 550
Scheme 2. Oxidation of alkyl ketene dimer 1 with cyclic diacyl peroxide 2 in the presence of trimethyl orthoformate.
Scheme 2. Oxidation of alkyl ketene dimer 1 with cyclic diacyl peroxide 2 in the presence of trimethyl orthoformate.
Molbank 2023 m1651 sch002
Molbank 2023 m1651 sch003 550
Scheme 3. Proposed mechanism of oxidation of alkyl ketene dimer 1 with cyclic diacyl peroxide 2 in the presence of trimethyl orthoformate.
Scheme 3. Proposed mechanism of oxidation of alkyl ketene dimer 1 with cyclic diacyl peroxide 2 in the presence of trimethyl orthoformate.
Molbank 2023 m1651 sch003
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MDPI and ACS Style

Gorlov, E.S.; Shuingalieva, D.V.; Ilovaisky, A.I.; Vil’, V.A.; Terent’ev, A.O. 1-(((6-(Methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic Acid. Molbank 2023, 2023, M1651. https://doi.org/10.3390/M1651

AMA Style

Gorlov ES, Shuingalieva DV, Ilovaisky AI, Vil’ VA, Terent’ev AO. 1-(((6-(Methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic Acid. Molbank. 2023; 2023(2):M1651. https://doi.org/10.3390/M1651

Chicago/Turabian Style

Gorlov, Evgenii S., Diana V. Shuingalieva, Alexey I. Ilovaisky, Vera A. Vil’, and Alexander O. Terent’ev. 2023. "1-(((6-(Methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic Acid" Molbank 2023, no. 2: M1651. https://doi.org/10.3390/M1651

APA Style

Gorlov, E. S., Shuingalieva, D. V., Ilovaisky, A. I., Vil’, V. A., & Terent’ev, A. O. (2023). 1-(((6-(Methoxycarbonyl)-5-oxononan-4-yl)oxy)carbonyl)cyclopropane-1-carboxylic Acid. Molbank, 2023(2), M1651. https://doi.org/10.3390/M1651

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