Supporting Information for Boiling Water-Catalyzed Neutral ... · Boiling Water-Catalyzed Neutral...
Transcript of Supporting Information for Boiling Water-Catalyzed Neutral ... · Boiling Water-Catalyzed Neutral...
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Supporting Information for
Boiling Water-Catalyzed Neutral and Selective N-Boc
Deprotection
Jia Wang, Yan-Liang Liang, Jin Qu*
The State Key Laboratory of Elemento-organic Chemistry,
Nankai University, Tianjin 300071, P. R. China
Fax: +86-(022)-23499247 and E-mail:[email protected]
Table of Contents
General.............................................................................................................................................2
General Procedure for N-Boc Deprotection Reaction in Boiling Water ....................................2
1H NMR Studies of the Deprotection of N-Boc-benzotriazole in D2O at 60oC ..........................3
Analytical Data for Compounds in Table 1 ..................................................................................4
Analytical Data for Compounds in Table 2 ..................................................................................6
Analytical Data for Compounds in Table 3 ..................................................................................9
Selected NMR Spectra ..................................................................................................................14
References ......................................................................................................................................18
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General
All reactions were carried out in aerial atmosphere, unless otherwise mentioned. Water was
purchased from Watson water or from Milli-Q® Ultrapure Water Purification System. Flash chromatography was performed on silica gel columns (200 – 300 mesh). All of the compounds were characterized by 1H NMR and 13C NMR. 1H NMR spectra were recorded at 300 MHz, 400 MHz or 600 MHz; 13C NMR were recorded at 75 MHz, 100 MHz or 150 MHz. Peaks recorded are relative to internal standards: TMS (δ = 0.00) for 1H and CDCl3 (δ = 77.00) for 13C spectra.
General Procedure for N-Boc Deprotection Reaction in Boiling Water
In a 50 mL round bottle flask filled with 20 mL of water, tert-butyl 3–(hydroxymethyl)
phenylcarbamate (223 mg, 1 mmol) was added. Then the flask topped with a condenser was dipped in a 110℃ oil bath. TLC was used to monitor the progress of the reaction. The reaction mixture was cooled down after 1.5 h and was extracted with ethyl acetate (40 mL×3). The extract was washed with brine, dried over anhydrous Na2SO4, and then concentrated in vacuum. The residue was purified by column chromatography on silica gel with ethyl acetate/petroleum ether (1:1, v/v) to afford the free amine as a colorless solid (120 mg, yield 98%, for most of cases, no further purification is needed). 1H NMR (400 MHz, CDCl3) δ 7.42 (s, 1H), 7.21–7.24 (m, 2H), 7.03 (d, J = 6.8 Hz, 1H), 6.56 (br s, 1H, NH), 4.65 (s, 2H), 1.95 (br s, 1H, OH), 1.51 (s, 9H)
Most of the substrate was insoluble in water at room temperature, but it became partially
soluble or completely miscible when temperature was raised above 60°C. For very sticky Nα,Nind-diBoc-tryptamine, the substrate was firstly dissolved in 1 mL of 1,4-dioxane and then 19 mL of water was added. We note that most organic compounds containing one or more hydrogen-bond-forming functional groups should have good solubility in hot water (60−100°C).
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1H NMR Studies of the Deprotection of N-Boc-benzotriazole in D2O at 60oC
The white solid of N-Boc-benzotriazole (100 mg) and 500 μL of D2O were placed in
an NMR tube and were sonicated for 1 minute at room temperature. There is no signal
in the 1H NMR spectrum recorded because N-Boc-benzotriazole is not soluble in pure
water at room temperature. The NMR tube was then immersed into a 60oC water bath
for 4 min (shake the NMR tube occasionally) and then was cooled down in an ice bath.
The peaks of N-Boc-benzotriazole appear in the 1H NMR spectrum were recorded
because N-Boc-benzotriazole is partially soluble in water after heating (in order to
insure that the signals in 1H NMR spectrum belong to the starting material, a 13C
NMR spectrum of the 4 min sample was also taken and compared with the 13C NMR
spectrum of N-Boc-benzotriazole taken in CDCl3). The high-field singlet attributes to
the t-butanol formed in the reaction. Similarly, the NMR tube was heated for another
4 minutes and was cooled down before the 1H NMR spectrum was recorded. On the 1H NMR spectrum, the signals of the product rise while the signals of the starting
material fall down. After the reaction finished (16 min), 20 mg of authentic t-butanol
was added in the NMR tube and it is found that the high field singlet do not split
which means it is the signal from t-butanol.
4 min
8 min12 min16 min
20 mg t -BuOH added
CH3 in t-BuOH
before heating
solvent peak of D2O
N
N
N
OO
H2O
NH
N
N
60oC
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Analytical Data for Compounds in Table 1
tert–Butyl 1H–imidazole–1–carboxylate 1
N
N
Boc
Table 1 - Entry 1
1H NMR (400 MHz, CDCl3) δ 8.08 (d, J = 2.4 Hz, 1H), 7.38 (s, 1H), 7.03 (d, J = 2.4 Hz, 1H), 1.63 (s, 9H) tert–Butyl 1H–pyrazole–1–carboxylate 2
NNBoc
Table 1 - Entry 2 1H NMR (400 MHz, CDCl3) δ 8.11 (d, J = 2.4 Hz, 1H), 7.72 (s, 1H), 6.39 (t, J = 2.8 Hz, 1H), 1.66 (s, 9H) tert–Butyl 1H–benzo[d]imidazole–1–carboxylate 3
N
N
BocTable 1 - Entry 3
1H NMR (600 MHz, CDCl3) δ 8.43 (s, 1H), 7.99 (d, J = 7.8 Hz, 1H), 7.79 (d, J = 7.8 Hz, 1H), 7.34–7.39 (m, 2H), 1.70 (s, 9H) tert–Butyl 1H–benzo[d][1,2,3]triazole–1–carboxylate 4
NN
NBoc
Table 1 - Entry 4 1H NMR (600 MHz, CDCl3) δ 8.12 (d, J = 8.4 Hz, 1H), 8.07 (d, J = 8.4 Hz, 1H), 7.63 (t, J = 7.8 Hz, 1H), 7.48 (t, J = 7.8 Hz, 1H), 1.77 (s, 9H)
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tert–Butyl 1H–indole–1–carboxylate 5
NBoc
Table 1 - Entry 5
1H NMR (600 MHz, CDCl3) δ 8.15 (m, 1H), 7.59 (s, 1H), 7.55 (d, J = 7.8 Hz, 1H), 7.30 (d, J = 7.8 Hz, 1H), 7.22 (m, 1H), 6.56 (s, 1H), 1.67 (s, 9H) tert–Butyl 1H–pyrrolo[2,3–b]pyridine–1–carboxylate 6
N NBoc
Table 1 - Entry 6
1H NMR (400 MHz, CDCl3) δ 8.51 (dd, J = 1.6, 4.8 Hz, 1H), 7.87 (dd, J = 1.6, 7.6 Hz, 1H), 7.64 (d, J = 4.0 Hz, 1H), 7.18 (dd, J = 4.8, 7.6 Hz, 1H), 6.50 (d, J = 4.0 Hz, 1H), 1.67 (s, 9H) tert–Butyl 3–acetyl–1H–indole–1–carboxylate 7
NBoc
Ac
Table 1 - Entry 7
1H NMR (600 MHz, CDCl3) δ 8.37 (m, 1H), 8.23 (s, 1H), 8.12 (m, 1H), 7.37 (m, 2H), 2.57 (s, 3H, CH3), 1.72 (s, 9H)
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Analytical Data for Compounds in Table 2
tert–Butyl phenylcarbamate 8
Table 2 - Entry 1
HN Boc
1H NMR (300 MHz, CDCl3) δ 7.39 (d, J = 8.0 Hz, 2H), 7.32 (t, J = 8.0 Hz, 2H), 7.03 (t, J = 7.2 Hz, 1H), 6.48 (s, 1H, NH), 1.52 (s, 9H) tert–Butyl p–tolylcarbamate 9
Table 2 - Entry 2
HN Boc
1H NMR (400 MHz, CDCl3) δ 7.23 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 8.4 Hz, 2H), 6.42 (br s, 1H, NH), 2.29 (s, 3H), 1.51 (s, 9H) tert–Butyl 4–chlorophenylcarbamate 10
Table 2 - Entry 3
HN BocCl
1H NMR (400 MHz, CDCl3) δ 7.31 (d, J = 8.8 Hz, 2H), 7.24 (d, J = 9.2 Hz, 2H), 6.53 (br s, 1H, NH), 1.51 (s, 9H) tert–Butyl 4–bromophenylcarbamate 9
Table 2 - Entry 4
HN BocBr
1H NMR (600 MHz, CDCl3) δ 7.38 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), 6.48 (br s, 1H, NH), 1.53 (s, 9H) tert–Butyl 4–hydroxyphenylcarbamate 9
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Table 2 - Entry 5
HN BocHO
1H NMR (600 MHz, CDCl3) δ 7.17 (d, J = 7.2 Hz, 2H), 6.73 (d, J = 7.2 Hz, 2H), 6.34 (br s, 1H, NH), 5.27 (br s, 1H, OH), 1.51 (s, 9H) tert–Butyl 3–hydroxyphenylcarbamate 11
Table 2 - Entry 6
HO
NH Boc
1H NMR (400 MHz, CDCl3) δ 7.11 (m, 2H), 6.72 (d, J = 7.6 Hz, 1H), 6.52 (t, J = 8.0 Hz, 2H), 5.39 (br s, 1H), 1.52 (s, 9H) tert–Butyl 4–methoxyphenylcarbamate 1
Table 2 - Entry 7
HN BocO
1H NMR (600 MHz, CDCl3) δ 7.25 (d, J = 9.0 Hz, 2H), 6.83 (d, J = 9.0 Hz, 2H), 6.35 (br s, 1H, NH), 3.78 (s, 3H), 1.51 (s, 9H) tert–Butyl 4–acetoxyphenylcarbamate 12
Table 2 - Entry 8
AcOHN Boc
1H NMR (300 MHz, CDCl3) δ 7.36 (d, J = 9.0 Hz, 2H), 7.01 (d, J = 8.7 Hz, 2H), 6.49 (br s, 1H, NH), 2.28 (s, 3H), 1.51 (s, 9H); 13C NMR (75 MHz, CDCl3) δ 188.62, 152.69, 146.04, 136.01, 121.93, 119.42, 80.65, 28.31, 21.04 tert–Butyl 3–(hydroxymethyl)phenylcarbamate 13
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Table 2 - Entry 9
OH
NH Boc
1H NMR (400 MHz, CDCl3) δ 7.42 (s, 1H), 7.21–7.24 (m, 2H), 7.03 (d, J = 6.8 Hz, 1H), 6.56 (br s, 1H, NH), 4.65 (s, 2H), 1.95 (br s, 1H, OH), 1.51 (s, 9H) tert–Butyl 4–acetylphenylcarbamate 14
Table 2 - Entry 10
AcHN Boc
1H NMR (300 MHz, CDCl3) δ 7.81 (d, J = 8.7 Hz, 2H), 7.43 (d, J = 8.1 Hz, 2H), 6.55 (s, 1H, NH), 2.47 (s, 3H), 1.41 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 197.12, 152.31, 143.26, 131.36, 129.67, 117.34, 80.88, 28.09, 26.20 tert–Butyl 4–nitrophenylcarbamate 1
Table 2 - Entry 11
HN BocO2N
1H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 9.2 Hz, 2H), 7.54 (d, J = 9.2 Hz, 2H), 6.96 (br s, 1H, NH), 1.54 (s, 9H) tert–Butyl 4–(dimethylamino)phenylcarbamate 15
Table 2 - Entry 12
HNN Boc
1H NMR (400 MHz, CDCl3) δ 7.21 (d, J = 6.4 Hz, 2H), 6.70 (t, J = 6.4 Hz, 2H), 6.25 (br s, 1H, NH), 2.89 (s, 6H), 1.50 (s, 9H)
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Analytical Data for Compounds in Table 3
tert–Butyl Butylcarbamate 3
NH
Boc
Table 3 - Entry 1 - Substrate
1H NMR (400 MHz, CDCl3) δ 4.52 (s, 1H, NH), 2.74-2.75 (m, 2H), 1.08 (s, 9H), 1.07-1.11 (m,
2H), 0.95-1.01 (m, 2H), 0.55 (t, J = 0.8 Hz, 3H)
tert–Butyl 5–hydroxypentylcarbamate 16
Table 3 - Entry 2 - Substrate
BocHN OH
1H NMR (600 MHz, CDCl3) δ 4.68 (s, 1H, NH), 3.64 (t, J = 6.0 Hz, 3H), 3.12 (br, 2H), 2.08–2.19 (m, 1H), 1.57–1.60 (m, 2H), 1.50–1.52 (m, 2H), 1.44 (s, 9H), 1.38–1.41 (m, 2H); 13C NMR (150 MHz, CDCl3) δ 156.08, 79.06, 62.53, 40.36, 32.19, 29.79, 28.37, 22.87 tert–Butyl 2–hydroxycyclohexylcarbamate 17
Table 3 - Entry 3 - Substrate
HN
OH
Boc
trans
1H NMR (400 MHz, CDCl3) δ 4.61 (br s, 1H), 3.30 (br s, 3H), 1.95–2.05 (m, 2H), 1.68–1.70 (m, 2H), 1.45 (s, 9H), 1.12–1.30 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 157.12, 79.85, 75.13, 56.52, 34.08, 31.72, 28.31, 24.64, 24.00 tert–Butyl 4–hydroxypiperidine–1–carboxylate 18
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Table 3 - Entry 4 - Substrate
N
OH
Boc
1H NMR (600 MHz, CDCl3) δ 3.80–3.88 (m, 3H), 3.03 (m, 2H), 1.83–1.88 (m, 2H), 1.67 (br s, 1H, OH), 1.46 (s, 9H), 1.39–1.54 (m, 2H); 13C NMR (150 MHz, CDCl3) δ 154.80, 79.52, 67.71, 41.23, 34.14, 28.40 tert-Butyl 2-oxopiperidine-1-carboxylate 19
Table 3 - Entry 5 - Substrate
N
O
Boc
1H NMR (600 MHz, CDCl3) δ 3.52−3.58 (m, 2H), 2.35−2.46 (m, 2H), 1.67−1.77 (m, 4H), 1.42 (s, 9H); 13C NMR (150 MHz, CDCl3) δ 171.15, 152.45, 82.54, 46.12, 34.68, 27.79, 25.57, 20.28 tert–Butyl (S)–1–(methoxycarbonyl)ethylcarbamate 20
1H NMR (400 MHz, CDCl3) δ 5.05 (br, 1H), 4.32 (m, 1H), 3.75 (s, 3H), 1.45 (s, 9H), 1.38 (d, J = 6.4 Hz, 3H); 13C NMR (150 MHz, CDCl3) δ 173.80, 155.06, 79.77, 52.24, 49.10, 28.26, 18.59 tert–Butyl (S)–1–(cyclohexylcarbamoyl)–2–hydroxyethylcarbamate 21
Table 3 - Entry 8 - Substrate
HN
OH
NH
O
Boc
1H NMR (300 MHz, CDCl3) δ 6.72 (s, 1H, NH), 5.70 (s, 1H), 4.04–4.13 (m, 2H), 3.70–3.76 (m, 2H), 3.64 (s, 1H), 1.46 (s, 9H), 1.17–2.07 (m, 10H); 13C NMR (75 MHz, CDCl3) δ 170.45, 156.33, 80.47, 62.85, 54.81, 54.76, 48.13, 32.68, 28.26, 25.43, 25.51
Table 3 - Entry 7 - Substrate
HN
O
O
Boc
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(S)–2–amino–N–cyclohexyl–3–hydroxypropanamide 22
Table 3 - Entry 8 - Product
H2N
OH
NH
O
1H NMR (300 MHz, CDCl3) δ 7.37–7.39 (br s, 1H), 3.72–3.82 (br, 3H), 3.43 (t, J = 4.8 Hz, 1H), 2.62 (br s, 4H), 1.13–2.05 (m, 9H); 13C NMR (75 MHz, CDCl3) δ 172.63, 65.30, 55.86, 47.81, 32.98, 32.87, 25.46, 24.72 tert–Butyl 2–(1–(tert–butoxycarbonyl)–1H–imidazol–5–yl)ethylcarbamate 23
Table 3 - Entry 9 - SubstrateN
N
HN BocBoc
1H NMR (400 MHz, CDCl3) δ 8.01 (s, 1H), 7.14 (s, 1H), 5.02 (br s, 1H, NH), 3.43 (t, J = 6.3 Hz, 2H), 2.74 (t, J = 6.6 Hz, 2H), 1.61 (s, 9H), 1.44 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 155.89, 146.99, 141.20, 136.78, 113.65, 85.36, 79.04, 39.80, 28.37, 28.29, 27.86 tert–Butyl 2–(1H–imidazol–5–yl)ethylcarbamate 24
Table 3 - Entry 9 - ProductN
HN
HN Boc
1H NMR (400 MHz, CDCl3) δ 11.07 (s, 1H), 7.53 (s, 1H), 6.74 (s, 1H), 5.35 (s, 1H, NH), 3.30 (s, 2H), 2.72 (s, 2H), 1.33 (s, 9H); 13C NMR (150 MHz, CDCl3) δ 156.06, 134.72, 116.77, 99.80, 78.92, 40.20, 28.16, 27.24 tert–Butyl 2–(1–(tert–butoxycarbonyl)–1H–indol–3–yl)ethylcarbamate 25
Table 3 - Entry 10 - Substrate
N
NH
Boc
Boc
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1H NMR (600 MHz, CDCl3) δ 8.14 (d, J = 8.0 Hz, 1H), 7.52 (d, J = 7.8 Hz, 1H), 7.41 (s, 1H), 7.30 (t, J = 7.2 Hz, 1H), 7.21 (t, J = 7.2 Hz, 1H), 4.85 (br s, 1H, NH), 3.44 (s, 2H), 2.87 (s, 2H), 1.65 (s, 9H), 1.43 (s, 9H); 13C NMR (150 MHz, CDCl3) δ 155.77, 149.49, 135.39, 130.29, 124.23, 122.92, 122.28, 118.77, 117.65, 115.08, 83.22, 78.90, 40.07, 29.50, 28.22, 27.99 tert–Butyl 2–(1H–indol–3–yl)ethylcarbamate 26
NH
NH O
O
Table 3 - Entry 10 - Product
1H NMR (600 MHz, CDCl3) δ 8.08 (s, 1H), 7.61 (d, J = 7.8 Hz, 1H), 7.37 (d, J = 7.8 Hz, 1H), 7.20 (t, J = 7.2 Hz, 1H), 7.12 (t, J = 7.8 Hz, 1H), 7.03 (s, 1H), 4.62 (s, 1H), 3.47 (d, J = 6.0 Hz, 2H), 2.96 (t, J = 6.0 Hz, 2H), 1.44 (s, 9H); 13C NMR (150 MHz, CDCl3) δ 156.06, 136.43, 127.37, 122.01, 119.30, 118.72, 112.99, 112.93, 111.19, 79.24, 41.07, 28.41, 25.81 (S)-tert-Butyl 2-(butyl-tert-Butoxycarbonylcarbamoyl)pyrrolidine-1-carboxylate
NN
OBoc
Boc
Table 3 - Entry 11 - Substrate 1H NMR (600 MHz, CDCl3) δ 5.18-5.22 (m, 1H), 3.58-3.75 (m, 3H), 3.42-3.50 (m, 1H), 2.32 (s, 1H), 1.86-1.95 (m, 3H), 1.56 (s, 5H), 1.54 (s, 4H), 1.47 (s, 4H), 1.40 (s, 5H), 1.27-1.36 (m, 4H), 0.91-0.96 (m, 3H); 13C NMR (150 MHz, CDCl3) δ 175.73, 175.39, 154.10, 153.42, 152.79, 152.59, 82.73, 82.48, 78.90, 78.87, 61.01, 60.54, 46.65, 46.35, 44.26, 44.21, 30.91, 30.57, 30.40, 30.25, 28.18, 28.00, 27.69, 23.28, 27.72, 19.78, 19.73, 13.53, 13.50 (cis/trans=1:1); LRMS (ESI) [M+H]+ m/z 371.0; HRMS (ESI) for C19H34N2O5: Calcd for [M+H]+ m/z 371.2573, found 371.2579. (S)-tert-Butyl 2-(butylcarbamoyl)pyrrolidine-1-carboxylate 27
N
HN
OBocTable 3 - Entry 11 - Product
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1H NMR (600 MHz, CDCl3) δ 6.85 (s, 0.5H), 6.42 (s, 0.5H), 3.93-4.00 (m, 1H), 2.93-3.19 (m, 4H), 1.60-1.99 (m, 4H), 1.19 (s, 9H), 1.08-1.09 (m, 4H), 0.65 (m, 3H); 13C NMR (150 MHz, CDCl3) δ 171.58, 171.55, 155.08, 154.11, 99.70, 79.59, 60.63, 59.77, 46.54, 38.51, 31.23, 31.19, 31.06, 30.72, 27.83, 24.02, 23.20, 19.48, 13.19 (cis/trans=1:1)
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Selected NMR Spectra
tert–Butyl 2–(1H–imidazol–5–yl)ethylcarbamate 1H NMR
ppm (t1)0.05.010.0
0
10000
20000
30000
40000
50000
60000
11.9
02
7.52
4
6.76
5
5.37
9
3.33
4
2.74
3
1.35
3
1.00
0.99
1.00
0.90
2.03
2.01
9.04
HNN
HNBoc
1H NMR, 600MHz, CDCl3
tert–Butyl 2–(1H–imidazol–5–yl)ethylcarbamate 13C NMR
ppm (t1)050100150
0
10000
20000
30000
40000
50000
60000
156.
061
134.
722
116.
765
99.7
96
78.9
24
77.2
1277
.000
76.7
88
40.2
01
28.1
5927
.244
HNN
HNBoc
13C NMR, 150MHz, CDCl3
solvent peak solvent peak
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tert–Butyl 2–(1H–indol–3–yl)ethylcarbamate 1H NMR
ppm (t1)0.05.010.0
0
50000
10000
15000
20000
250008.
372
8.36
68.
362
8.36
08.
356
8.35
48.
351
8.34
88.
347
8.34
38.
342
7.63
8
7.38
77.
272
7.23
77.
227
7.16
07.
149
7.01
1
4.67
14.
668
4.66
64.
664
4.66
34.
655
4.64
2
3.49
3
2.98
72.
979
1.48
5
9.00
0.88
1.00
1.021.001.021.00
0.87
2.02
2.04
NH
NH
Boc
1H NMR,600MHz,CDCl3
tert–Butyl 2–(1H–indol–3–yl)ethylcarbamate 13C NMR
ppm (t1)050100150200
0
10000
20000
30000
40000
50000
60000
156.
062
136.
426
127.
368
122.
009
119.
298
118.
718
112.
986
112.
930
111.
188
79.2
4277
.212
77.0
0076
.788
41.0
72
28.4
0525
.811
NH
NH
Boc
13C NMR,150MHz,CDCl3
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(S)-tert-Butyl 2-(butyl-tert-Butoxycarbonylcarbamoyl)pyrrolidine-1-carboxylate 1H NMR
ppm (t1)1.02.03.04.05.0
0
50000
10000
5.22
15.
207
5.19
05.
176
4.14
84.
136
4.12
44.
112
3.74
73.
732
3.71
13.
699
3.68
43.
669
3.65
83.
646
3.63
53.
626
3.60
43.
595
3.58
23.
504
3.49
33.
480
3.47
73.
466
3.44
73.
434
3.42
22.
323
2.31
8
2.05
01.
952
1.93
81.
926
1.89
41.
873
1.86
81.
861
1.56
11.
535
1.46
81.
400
1.36
01.
349
1.33
81.
327
1.31
51.
271
0.96
00
925
091
3
3.05
1.00
3.08
1.00
0.96
2.88
4.02
4.994.064.004.99
NN
O
BocBoc
1H NMR, 600MHz, CDCl3
(S)-tert-Butyl 2-(butyl-tert-Butoxycarbonylcarbamoyl)pyrrolidine-1-carboxylate 13C NMR
ppm (t1)050100150200
0
10000
20000
30000
40000
50000
60000
70000
80000175.
727
175.
388
154.
095
153.
418
152.
789
152.
593
82.7
2982
.482
78.9
0278
.866
77.2
1377
.000
76.7
8761
.010
60.5
3546
.653
46.3
4944
.263
44.2
1030
.905
30.5
7430
.404
30.2
4928
.184
27.9
9527
.687
23.2
8122
.724
19.7
7719
732
NN
O
BocBoc
13C NMR, 150MHz, CDCl3
Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2009
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(S)-tert-Butyl 2-(butylcarbamoyl)pyrrolidine-1-carboxylate 1H NMR
ppm (t1)0.05.0
0
10000
20000
30000
40000
6.84
7
6.42
0
3.99
93.
932
3.19
23.
053
3.04
93.
007
2.99
12.
929
1.98
6
1.90
31.
789
1.76
81.
665
1.59
51.
189
1.08
41.
075
0.64
7
3.00
0.97
4.08
4.07
9.003.99
0.46
0.42
NNH
O
Boc1H NMR, 600MHz, CDCl3
(S)-tert-Butyl 2-(butylcarbamoyl)pyrrolidine-1-carboxylate 13C NMR
ppm (t1)050100150
0
50000
10000
15000
20000
25000
171.
584
171.
554
155.
076
154.
105
99.6
98
79.5
9277
.213
77.0
0076
.786
60.6
3259
.768
46.5
3638
.511
31.2
3331
.194
31.0
5830
.718
27.8
2624
.020
23.1
9619
.482
13.1
87
NNH
O
Boc13C NMR, 150MHz, CDCl3
Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2009
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Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2009