Efficient Brønsted
Acid Catalyzed Hydrations and Hydroaminations of (Dicyclopropylmethylene)cyclopropane

Lutz Ackermann; Sergei I. Kozhushkov; Dmitry S. Yufit; Ilan Marek

doi:10.1055/s-0030-1260769

LETTER

Efficient Brønsted Acid Catalyzed Hydrations and Hydroaminations of (Dicyclopropylmethylene)cyclopropane

Lutz Ackermann*^a, Sergei I. Kozhushkov^a, Dmitry S. Yufit^b, Ilan Marek^c
^a Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstr. 2, 37077 Göttingen, Germany
Fax: +49(551)396777; e-Mail: lutz.ackermann@chemie.uni-goettingen.de;
^b Department of Chemistry, University of Durham, Durham, South Rd., DH1 3LE, UK
^c Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel

Abstract

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Abstract

(Dicyclopropylmethylene)cyclopropane underwent efficient Brønsted acid catalyzed hydrations and hydroaminations with H₂O and basic amines, respectively, occurring with conservation of all three cyclopropane rings.

Key words

Brønsted acids - catalysis - hydroaminations - methylenecyclopropanes - ring conservation

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References

References and Notes

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17a ^¹H NMR and ^¹³C NMR spectra of 2 were identical to those of an independently prepared sample, following a published procedure. See: Hanack M. Eggensperger H. Liebigs Ann. Chem. 1963, 663: 31

17b

Compound 2: ^¹H NMR (250 MHz, CDCl₃): δ = 1.61 (s, 1 H), 0.79-0.90 (m, 3 H), 0.43-0.49 (m, 6 H), 0.29-0.40 (m, 6 H). ^¹³C NMR (62.9 MHz, CDCl₃): δ = 69.7 (C), 18.7 (CH), -0.1 (CH₂). [D]₁-2: ^¹H NMR (250 MHz, CDCl₃): δ = 1.60 (s, 1 H), 0.79-0.91 (m, 2 H), 0.43-0.49 (m, 6 H), 0.28-0.40 (m, 6 H). ^¹³C NMR (62.9 MHz, CDCl₃): δ = 69.7 (C), 18.7 (CD), 18.3 (t, J = 24.0 Hz, CH), -0.1 (CH₂), -0.2 (CH₂).

18 The use of pure HCl as the catalyst may result in ring-opening reactions even under mild reaction conditions: Donskaya NA. Shulishov EV. Shabarov YS. Zh. Org. Khim. 1981, 17: 2102

19

However, traces (<5%) of a ring-opened product were detected in the ^¹H NMR spectrum of crude product 7b.

20

General Procedure for the Preparation of Benzyl(tricyclopropylmethyl)amine (7a), Phenethyl(tricyclopropylmethyl)amine (7b) and n -Octyl(tricyclopropylmethyl)amine (7c): A flame-dried Schlenk flask was cooled and charged with 1, (402.6 mg, 442.1 µL, 3.0 mmol), the corresponding amine (1.0 equiv) and NH₄Cl (16.0 mg, 10 mol%) in anhyd 1,4-dioxane (3.0 mL) under Ar. After stirring the reaction mixture for 48 h at 120 ˚C, Et₂O (50 mL) was added at ambient temperature, and the reaction mixture was extracted with aq HCl (0.1 N, 2 × 80 mL). The combined aqueous phases were washed with Et₂O (2 × 50 mL) and, after addition of aq NaOH (1 N, 25 mL), extracted with CH₂Cl₂ (3 × 40 mL). The combined organic phases were dried over K₂CO₃ and concentrated under reduced pressure. The residue was dissolved in MeOH (20 mL), stirred with charcoal (2.0 g) at ambient temperature overnight, quickly filtered through a thin pad of silica gel and concentrated in vacuo. Amines 7a-c (1.0 mmol) were dissolved in CH₂Cl₂ (5.0 mL), and a solution of p-TsOH˙H₂O (190.2 mg, 1.0 mmol, 1.0 equiv) in MeOH (2.0 mL) was added in one portion at ambient temperature. After an additional stirring for 10 min, the reaction mixture was evaporated, and the corresponding p-toluenesulfonate was purified by slow evaporation of its solution in CH₂Cl₂-octane (7a˙p-TsOH: 92% yield, and 7c˙p-TsOH: 94% yield) or in THF-octane (7b˙p-TsOH: 95% yield) at +4 ˚C. Compound 7a: colorless oil. ^¹H NMR (250 MHz, CDCl₃):
δ = 7.21-7.38 (m, 5 H), 3.98 (s, 2 H), 1.53 (br s, 1 H), 0.69-0.71 (m, 3 H), 0.48-0.53 (m, 6 H), 0.29-0.35 (m, 6 H). ^¹³C NMR (62.9 MHz, CDCl₃): δ = 142.3 (C), 128.0 (CH), 127.8 (CH), 126.6 (CH), 52.9 (C), 46.7 (CH₂), 15.9 (CH), 0.0 (CH₂). Compound 7a×p-TsOH: colorless crystals; mp 137-139 ˚C. ^¹H NMR (250 MHz, CDCl₃): δ = 8.34 (br s, 2 H), 7.65 (d, J = 8.0 Hz, 2 H), 7.52-7.56 (m, 2 H), 7.20-7.26 (m, 3 H), 7.16 (d, J = 8.0 Hz, 2 H), 4.29 (t, J = 5.6 Hz, 2 H), 2.37 (s, 3 H), 0.65-0.75 (m, 9 H), 0.40-0.47 (m, 6 H). ^¹³C NMR (62.9 MHz, CDCl₃): δ = 142.4 (C), 139.9 (C), 132.4 (C), 130.2 (CH), 128.6 (CH), 128.5 (CH), 128.4 (CH), 125.9 (CH), 67.0 (C), 46.5 (CH₂), 21.3 (Me), 11.5 (CH), 1.8 (CH₂). Compound 7b: colorless oil. ^¹H NMR (250 MHz, CDCl₃): δ = 7.17-7.29 (m, 5 H), 3.05 (t, J = 7.3 Hz, 2 H), 2.75 (t, J = 7.3 Hz, 2 H), 1.53 (br s, 1 H), 0.51-0.60 (m, 3 H), 0.36-0.42 (m, 6 H), 0.20-0.32 (m, 6 H). ^¹³C NMR (62.9 MHz, CDCl₃): δ = 140.6 (C), 128.7 (CH), 128.1 (CH), 125.8 (CH), 52.9 (C), 43.8 (CH₂), 37.5 (CH₂), 15.6 (CH), 0.0 (CH₂). Compound 7b˙p-TsOH: colorless crystals; mp 149-150 ˚C. ^¹H NMR (250 MHz, CDCl₃): δ = 8.48 (br s, 2 H), 7.80 (d, J = 8.0 Hz, 2 H), 7.12-7.26 (m, 7 H), 3.25-3.41 (m, 4 H), 2.38 (s, 3 H), 0.72-0.75 (m, 9 H), 0.41-0.46 (m, 6 H). ^¹³C NMR (62.9 MHz, CDCl₃): δ = 142.8 (C), 140.0 (C), 137.8 (C), 129.0 (CH), 128.8 (CH), 128.5 (CH), 126.6 (CH), 125.8 (CH), 65.2 (C), 43.9 (CH₂), 32.7 (CH₂), 21.3 (Me), 11.0 (CH), 1.4 (CH₂). Compound 7c: colorless oil. ^¹H NMR (250 MHz, CDCl₃): δ = 2.75 (t, J = 7.0 Hz, 2 H), 1.65 (br s, 1 H), 1.35-1.51 (m, 2 H), 1.27 (m, 10 H), 0.88 (t, J = 6.5 Hz, 3 H), 0.54-0.63 (m, 3 H), 0.37-0.45 (m, 6 H), 0.23-0.30 (m, 6 H). ^¹³C NMR (62.9 MHz, CDCl₃): δ = 42.4 (C), 31.8 (CH₂), 31.4 (CH₂), 29.6 (CH₂), 29.3 (CH₂), 27.5 (CH₂), 26.4 (CH₂), 22.6 (CH₂), 15.7 (CH), 14.1 (Me), 0.0 (CH₂). Compound 7c˙p-TsOH: colorless crystals; mp 159-161 ˚C. ^¹H NMR (250 MHz, CDCl₃): δ = 8.18 (br s, 2 H), 7.71 (d, J = 8.3 Hz, 2 H), 7.14 (d, J = 8.3 Hz, 2 H), 3.03 (m, 2 H), 2.35 (s, 3 H), 1.92 (m, 2 H), 1.22 (m, 10 H), 0.88 (t, J = 6.5 Hz, 3 H), 0.73-0.75 (m, 9 H), 0.42-0.50 (m, 6 H). ^¹³C NMR (62.9 MHz, CDCl₃): δ = 143.0 (C), 139.6 (C), 128.6 (CH), 125.7 (CH), 64.8 (C), 42.3 (CH₂), 31.8 (CH₂), 29.4 (CH₂), 29.2 (CH₂), 27.4 (CH₂), 26.4 (CH₂), 22.6 (CH₂), 21.3 (Me), 14.1 (Me), 11.0 (CH), 1.4 (CH₂).

21 Yang Y. Huang X. Synlett 2008, 1366

22

CCDC 821336 (7a˙p-TsOH), CCDC 821337 (7b˙p-TsOH) and CCDC 821338 (7c˙p-TsOH) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: +44 (1223)336033; or deposit@ccdc.cam.ac.uk].