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DOI: 10.1055/s-0030-1260769
Efficient Brønsted Acid Catalyzed Hydrations and Hydroaminations of (Dicyclopropylmethylene)cyclopropane
Publication History
Publication Date:
01 June 2011 (online)
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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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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
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References and Notes
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).
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].