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[ CAS No. 24424-99-5 ]

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Chemical Structure| 24424-99-5
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CAS No. :24424-99-5 MDL No. :MFCD00008805
Formula : C10H18O5 Boiling Point : 235.8°C at 760 mmHg
Linear Structure Formula :- InChI Key :N/A
M.W :218.25 g/mol Pubchem ID :90495
Synonyms :

Safety of [ 24424-99-5 ]

Signal Word:Danger Class:6.1,4.1
Precautionary Statements:P501-P260-P240-P210-P241-P271-P264-P280-P284-P302+P352-P370+P378-P337+P313-P305+P351+P338-P362+P364-P332+P313-P304+P340+P310-P403+P233-P405 UN#:2930
Hazard Statements:H330-H315-H319-H228 Packing Group:
GHS Pictogram:

Application In Synthesis of [ 24424-99-5 ]

  • Upstream synthesis route of [ 24424-99-5 ]
  • Downstream synthetic route of [ 24424-99-5 ]

[ 24424-99-5 ] Synthesis Path-Upstream   1~35

  • 1
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  • [ 75553-23-0 ]
  • [ 91-00-9 ]
  • [ 100564-78-1 ]
  • [ 82732-07-8 ]
Reference: [1] Tetrahedron Letters, 1993, vol. 34, # 48, p. 7781 - 7784
  • 2
  • [ 24424-99-5 ]
  • [ 102195-80-2 ]
Reference: [1] Chemistry - A European Journal, 2006, vol. 12, # 15, p. 4121 - 4143
[2] Tetrahedron Letters, 2003, vol. 44, # 42, p. 7809 - 7812
[3] Angewandte Chemie - International Edition, 2002, vol. 41, # 9, p. 1600 - 1602
[4] Journal of Organic Chemistry, 2001, vol. 66, # 10, p. 3593 - 3596
[5] Tetrahedron Letters, 1998, vol. 39, # 10, p. 1169 - 1172
[6] Tetrahedron Letters, 2012, vol. 53, # 30, p. 3847 - 3849
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[8] Patent: US2013/115194, 2013, A1,
[9] Patent: WO2015/155753, 2015, A2,
  • 3
  • [ 24424-99-5 ]
  • [ 102507-13-1 ]
Reference: [1] Angewandte Chemie - International Edition, 2014, vol. 53, # 18, p. 4642 - 4647[2] Angew. Chem., 2014, vol. 126, # 18, p. 4730 - 4735,6
  • 4
  • [ 2280-28-6 ]
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  • [ 102507-13-1 ]
Reference: [1] Tetrahedron Letters, 1986, vol. 27, # 25, p. 2789 - 2792
  • 5
  • [ 2280-27-5 ]
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  • [ 102507-13-1 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2004, vol. 14, # 16, p. 4329 - 4332
  • 6
  • [ 24424-99-5 ]
  • [ 101469-91-4 ]
  • [ 83220-73-9 ]
  • [ 101469-92-5 ]
Reference: [1] Synthetic Communications, 1985, vol. 15, # 7, p. 587 - 598
  • 7
  • [ 24424-99-5 ]
  • [ 124-68-5 ]
  • [ 102520-97-8 ]
YieldReaction ConditionsOperation in experiment
100% With triethylamine In dichloromethane at 20℃; for 2.83333 h; (3a)
(2-Hydroxy-1,1-dimethylethyl)carbamic acid t-butyl ester
230.4 ml of di-t-butyl dicarbonate (1.00 mol) was added to a solution of 98.05 g of 2-amino-2-methyl-1-propanol (1.10 mol) and 154 ml of triethylamine (1.10 mol) in methylene chloride (500 ml) at room temperature over 20 minutes, and the mixture was stirred at room temperature for 2.5 hours.
The reaction mixture was concentrated under reduced pressure and diluted with a 10percent citric acid aqueous solution, followed by extraction with ethyl acetate.
Then, the organic layer was washed with water and brine and dried over anhydrous magnesium sulfate.
After filtration, the solvent was evaporated under reduced pressure to obtain 189.25 g of the crude title compound (yield: quant.).
Colorless solid.
1H NMR spectrum (CDCl3, 400 MHz), δ: 4.64 (br s, 1H), 4.01 (br s, 1H), 3.59 (d, 2H, J = 6.3 Hz), 1.43 (s, 9H), 1.25 (s, 6H).
99% With iron(III) trifluoromethanesulfonate In neat (no solvent) at 20℃; for 0.0666667 h; Green chemistry General procedure: Fe(OTf)3 (1 molpercent) was added to a magnetically stirred mixture of anamine (1 mmol) and Boc2O (1 mmol) at room temperature. The mixturewas stirred until completion of the reaction (TLC), then diluted withEtOAc and washed with water. The organic layer was dried overanhydrous MgSO4, then the solvent was distillated off under vacuum toyield the highly pure N‑Boc derivatives
98% at 0 - 20℃; for 2 h; Di-tert-butyl dicarbonate (21.82 g, 100.00 mmol) was added in portions to a solution of 2- amino-2-methylpropan-i-ol (8.91 g, 100.0 mmol) in DCM (270 ml) at 0 °C. The reaction was stirred at room temperature for 2 hours, then was washed with 2N HC1 (100 mL). The organic phase was dried (MgSO4) and concentrated in vacuo to give tert-butyl (1-hydroxy- 2-methylpropan-2-yl)carbamate (18.56 g, 98 percent) as a white solid. ‘H NMR (400 MHz,CDC13, 27 °C) 1.25 (6H, s), 1.43 (9H, s), 3.58 (2H, d), 4.67 (1H, s).
97% With triethylamine In dichloromethane at 22 - 25℃; for 4 h; 2-Amino-2-methyl-l-propanol (5 g, 56.1 mmol), (Boc)20 (13.46 g, 61.7 mmol) and triethyl amine (6.24 g, 61.7 mmol) were dissolved in 50 mL of dichloromethane. The reaction mixture was stirred for 4 h at 22 to 25 °C. Above mixture was washed with water (25 mL x 2), dried over anhydrous sodium sulfate and concentrated under vacuum to get tert-buty] (1- hydroxy-2-methylpropan-2-yl)carbamate (10.3 g, 97percent yield).
90% With 1,3-disulfonic acid imidazolium hydrogen sulfate In neat (no solvent) at 20℃; for 0.0333333 h; Green chemistry General procedure: Amine (1 mmol) was added to the mixture of (Boc)2O (1 mmol) and DSIMHS (6.5 mg, ~ 0.02 mmol) with constant stirring at room temperature under solvent-free conditions. After completion of the reaction (monitored by TLC),   ethyl acetate (3 × 5 mL) was added to the reaction mixture and the catalyst was decanted and washed with ethyl acetate (2 × 5 mL) and dried. The product was purified by column chromatography, using   ethyl acetate–petroleum ether (2:8) eluent.
75.36% With triethylamine In dichloromethane at 0 - 20℃; for 1 h; To a solution of compound 1 (10.00 g, 112.18 mmol, 1.00 Eq) in DCM (200 mL) was added Et3N (23.00 g, 227.30 mmol, 2.03 Eq). The mixture was cooled to 0° C. and Boc2O (38.40 g, 175.95 mmol, 1.57 Eq) was added, the mixture was stirred at 20° C. for 1 hr. The mixture was diluted with EA and washed with water. The organic phase was concentrated in vacuo. The residue was purified by silica gel chromatography (Petroleum ether/Ethyl acetate=15/1) to afford compound 2 (16.00 g, 84.54 mmol, 75.36percent yield) as white solid.
75.36% With triethylamine In dichloromethane at 0 - 20℃; for 0.5 h; To a solution of compound 1 (10.00 g, 112.18 mmol, 1.00 Eq) in DCM (200 mL) was added Et3N (23.00 g, 227.30 mmol, 2.03 Eq). The mixture was cooled to 0° C. and Boc2O (38.40 g, 175.95 mmol, 1.57 Eq) was added, the mixture was stirred at 20° C. for 1 hr. The mixture was diluted with EA and washed with water. The organic phase was concentrated in vacuo. The residue was purified by silica gel chromatography (Petroleum ether/Ethyl acetate=15/1) to afford compound 2 (16.00 g, 84.54 mmol, 75.36percent yield) as white solid.
68% at 20℃; Example 4
(tert-Butoxy)-N-(1-hydroxy-2-methylpropyl)carboxamide (4)
Following the general procedure for the N-Boc-protection of ω-amino-2,2-dimethylalcohols of Description 2, 1.783 g (20.0 mmol) of 2-amino-2-methyl-1-propanol was reacted with 3.274 g (15.0 mmol) of di-tert-butyl-dicarbonate in a mixture of 20 mL of a saturated aqueous solution of sodium bicarbonate (NaHCO3) and 40 mL of acetonitrile to provide 1.937 g (68percent yield) of the title compound (4) as a colorless solid of sufficient purity to be used in subsequent steps without further isolation and purification. 1H NMR (400 MHz, CDCl3): δ=1.26 (s, 6H), 1.44 (s, 9H), 3.59 (d, J=6.0 Hz, 2H), 4.00-4.20 (br. m, 1H), 4.64-4.72 (br. m, 1H) ppm. MS (ESI) m/z 212.92 (M+Na)+.
53% at 25℃; for 1 h; 2-Amino-2-methyl-propan-1-ol (53 g, 0.59 mol) and di-tert-butyl dicarbonate (65.0 g, 0.297 mol) were combined in H2O (500 mL) and stirred at 25 °C for 1 h. The reaction mixture was extracted with CHCl3 (2 x 250 mL). The organics were dried and concentrated to a white amorphous solid which was recrystallized from hot hexanes to afford desired material (30 g, 53percent) as a white solid: 13C NMR (CD3OD, 100 MHz) δ 157.76, 80.135, 70.095, 54.992, 29.247, 24.695.
750 g With sodium hydrogencarbonate; sodium carbonate In tetrahydrofuran; water at 0 - 20℃; for 18 h; Intermediate 12: tert-butyl (l-hydroxy-2-meth lpropan-2-yl)carbamate - Preparation 2
To a solution of 2-amino-2-methylpropan-l-ol (500 g, 5.61 mol, Alfa) in THF (3.0 L) and water (1.0 L) was added Na2C03 (10.11 g, 95 mmol) and sodium bicarbonate (10.37 g, 123 mmol) and stirring continued at 0 QC. di-ferf-Butyl dicarbonate (1.56 L, 6.7 mol) was added. The reaction mixture was stirred at RT for 18 h. The THF layer was separated and the aqueous layer extracted with ethyl acetate (1.5 L). The combined organic layers were washed with brine solution (2 x 2 L), were dried over anhydrous Na2S04 and then concentrated under reduced pressure to afford crude title compound. The crude material was dissolved in petroleum ether (750 mL) and cooled to -50 °C. The resulting solid was filtered and washed with petroleum ether to give the title compound (750 g) as a white solid. (0250) *H NMR (400 MHz, DMSO-d6) δ: 6.08 (1H, s), 4.67 (1H, t), 3.29 (2H, s), 1.37 (9H, s), 1.13 (6H, s).

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  • 8
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Reference: [1] Patent: US6284764, 2001, B1,
  • 9
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  • 10
  • [ 775-16-6 ]
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  • [ 101385-93-7 ]
Reference: [1] Patent: WO2005/77924, 2005, A1, . Location in patent: Page/Page column 71-72
  • 11
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Reference: [1] Bioorganic and Medicinal Chemistry, 2007, vol. 15, # 2, p. 1022 - 1033
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[5] Patent: US2016/96837, 2016, A1,
[6] Patent: WO2017/17630, 2017, A1,
[7] Patent: EP3239143, 2017, A2,
[8] Patent: EP3269715, 2018, A1,
[9] Patent: EP1550660, 2005, A1,
  • 12
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  • [ 101385-93-7 ]
Reference: [1] Angewandte Chemie - International Edition, 2017, vol. 56, # 48, p. 15274 - 15278[2] Angew. Chem., 2017, vol. 129, p. 15476 - 15480,5
  • 13
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  • [ 24424-99-5 ]
  • [ 101187-40-0 ]
YieldReaction ConditionsOperation in experiment
100% at 0 - 20℃; for 23 h; Inert atmosphere General procedure: The diamine 10 (1 equiv) in DCM solution (10 mL / mmol) was treated with Boc2O in default (0.15 equiv) for 5 h at 0 °C and 18 h at room temperature. The organic phase was washed with water, until all the unreacted 10 was extracted. The Boc-protected compound 11 was quantitatively recovered after drying (MgSO4) and concentration under vacuum. 11a: 1H NMR (300 MHz, CDCl3): d 1.45 (s, 9H), 1.80 (br m, 2H, NH2), 3.25 (m, 2H), 3.38 (m, 2H), 3.50-3.70 (m, 8H), 5.10 (br s, 1H, NHCO2). 11b: 1H NMR (300 MHz, CDCl3): d 1.42 (s, 9H), 1.75 (br m, 2H, NH2), 2.84 (t, 2H, J = 5.3 Hz), 3.29 (m, 2H), 3.51 (m, 4H), 3.58 (sharp m, 8H), 5.30 (br s, 1H, NHCO2).
Reference: [1] Tetrahedron, 2012, vol. 68, # 52, p. 10818 - 10826
[2] Journal of the American Chemical Society, 2001, vol. 123, # 37, p. 8914 - 8922
[3] Bioorganic and Medicinal Chemistry, 2002, vol. 10, # 3, p. 625 - 637
[4] Bioorganic and Medicinal Chemistry Letters, 2002, vol. 12, # 6, p. 853 - 856
[5] Journal of the American Chemical Society, 2015, vol. 137, # 28, p. 9108 - 9116
[6] Patent: EP1783137, 2007, A1, . Location in patent: Page/Page column 24
[7] Patent: US2018/169262, 2018, A1, . Location in patent: Paragraph 0173; 0174
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Reference: [1] Patent: US2012/121615, 2012, A1,
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  • [ 101187-40-0 ]
Reference: [1] Patent: EP3173408, 2017, A1,
  • 16
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  • [ 101555-60-6 ]
YieldReaction ConditionsOperation in experiment
65%
Stage #1: With sodium hydroxide In water; acetone at 0 - 20℃;
Stage #2: With hydrogenchloride In water at 0℃;
(R)-2-Carboxymethyl-pyrrolidine-1-carboxylic acid tert-butyl ester: At about 0° C., a 5percent sodium hydroxide solution was added dropwise to a solution of (R)-2-(pyrrolidin-2-yl)acetic acid hydrochloride (3.00 g, 18.18 mmol) in water (30 mL). After diluting the solution with acetone (30 mL), di-tert-butyl dicarbonate (5.94 g, 27.27 mmol) was added dropwise. The resulting mixture was stirred at ambient temperature for about 6 hours and the acetone was removed in vacuo. The pH was adjusted to 3 by adding 3M hydrochloric acid dropwise, at about 0° C. Following standard extractive workup with ethyl acetate, the crude residue was purified by silica gel column chromatography (10percent ethyl acetate in chloroform) to yield the title product as an off-white solid (2.70 g, 65percent). m.p. 98-102° C.; [α]D20 +33.8° (c 2.0, DMF); 1H NMR (400 MHz, DMSO-d6) δ 1.37 (s, 3H), 1.60-1.85 (m, 3H), 1.90-2.00 (m, 1H), 2.14-2.27 (m, 1H); 2.54-2.93 (m, 1H), 3.15-3.24 (m, 2H), 3.87-3.95 (m, 1H), 12.13 (s, 1H, exchangeable with deuterium oxide); IR (KBr) υ 3184, 2976, 2882, 1736, 1656, 1421 cm-1; MS 228 (M-1).
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Reference: [1] European Journal of Medicinal Chemistry, 2011, vol. 46, # 8, p. 3455 - 3461
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  • [ 1001635-01-3 ]
Reference: [1] Tetrahedron Asymmetry, 2001, vol. 12, # 12, p. 1793 - 1799
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  • [ 100927-10-4 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 8, p. 2877 - 2879
[2] Patent: US2016/75720, 2016, A1,
  • 20
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  • [ 76179-40-3 ]
  • [ 1000698-88-3 ]
YieldReaction ConditionsOperation in experiment
74.2% With iodine In ethanol at 0℃; Example 54; N-Cyclohexyl-2-[5,6-difluoro-2-(methoxy-phenyl-methyl)-benzoimidazol-1-yl]-2-(4-methoxy-phenyl)-acetamide; Step 1; (2-Amino-4,5-difluoro-phenyl)-carbamic acid tert-butyl ester [CAS RN 1000698-88-3] (for alternative preparation see also Example 1, Step 1); To a ice-bath cooled mixture of 1,2-diamino-4,5-difluorobenzene (10.00 g, 69 mmol, 1.0 equiv., [CAS RN 76179-40-3]) and di-tert-butyl-dicarbonate (12.87 g, 59 mmol, 0.85 equiv; [CAS RN 24424-99-5]) in absolute ethanol (150 mL) was added iodine (0.18 g, 0.007 mmol, 0.01 equiv; [CAS RN 7553-56-2]). The mixture was maintained overnight in the refrigerator. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel (500 g, 1:0-->19:1 dichloromethane/ethyl acetate eluant) to afford, in order of elution, the bis-boc derivative as an orange solid (1.58 g, 6.6percent), and the desired compound as a white solid (12.58 g, 74.2percent).
74% With iodine In ethanolCooling with ice To a cooled (ice-bath) mixture of l,2-diamino-4,5-difluorobenzene (10.00 g, 69 mmol, 1.0 equiv., [CAS RN 76179-40-3]) and di-tert-butyl-dicarbonate (12.87 g, 59 mmol, 0.85 equiv; [CAS RN 24424-99-5]) in absolute ethanol (150ml) was added iodine (0.18g, 0.007 mmol, 0.01 equiv. [CAS RN 7553-56-2]). The mixture was maintained overnight in the refrigerator. The solvent was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel (50Og, 1:0 to 19:1 CH2Cl2/AcOEt eluant) to afford, in order of elution, the bis-boc derivative as an orange solid (1.58 g, 6 percent), and the desired compound as a white solid (12.58g, 740Zo)11H NMR (300 MHz, DMSO): <5 1.46 ( s, 9H), 5.03 (br s, 2H), 6.65 (dd, / = 8.2 Hz, / = 12.9 Hz, IH), 7.30 (dd, / = 8.9 Hz, / = 12.3 Hz, IH), 8.38 (br s, IH). MS (ISN): 243.4 [M-H]".
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  • [ 1000698-88-3 ]
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  • [ 1000068-25-6 ]
Reference: [1] Patent: WO2014/123794, 2014, A1,
[2] Patent: WO2014/123793, 2014, A1,
[3] Patent: US2014/213571, 2014, A1,
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[5] Patent: WO2014/121418, 2014, A1,
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  • [ 1000068-25-6 ]
Reference: [1] Patent: WO2014/205592, 2014, A1,
[2] Patent: WO2014/209729, 2014, A1,
[3] Organic Process Research and Development, 2016, vol. 20, # 7, p. 1227 - 1238
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  • [ 1001353-87-2 ]
Reference: [1] Patent: US2008/9497, 2008, A1,
[2] Patent: WO2014/82380, 2014, A1,
[3] Patent: CN103880823, 2017, B,
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  • [ 1001419-35-7 ]
Reference: [1] Patent: WO2011/130459, 2011, A1,
[2] Patent: WO2017/66606, 2017, A1,
[3] Journal of the American Chemical Society, 2017, vol. 139, # 21, p. 7318 - 7334
[4] Patent: WO2018/191394, 2018, A1,
  • 26
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  • [ 28121-73-5 ]
  • [ 1005187-65-4 ]
YieldReaction ConditionsOperation in experiment
84% With triethylamine In 1,2-dimethoxyethane at 20℃; A mixture of A-2 (6.07g, 20 rnmol), dk-butyl dicarbonate (1.7.4 g, BOmrnol),triethylamine (3.0 mL, 20mmol) and DMAP (30 mg) in dry DME (200ml) was stirred at room temperature over night. The solvent was removed. Solid was filtered and washed with diethyl ether to yield white solid, Yield: 8.5 g (84percent)
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  • [ 1010086-31-3 ]
Reference: [1] Patent: US2008/58347, 2008, A1, . Location in patent: Page/Page column 62
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  • [ 1007882-58-7 ]
Reference: [1] Patent: EP2730572, 2014, A1,
  • 29
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  • [ 1021918-86-4 ]
Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2011, vol. 21, # 22, p. 6793 - 6799
[2] Patent: WO2011/66211, 2011, A1,
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  • [ 1016258-66-4 ]
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YieldReaction ConditionsOperation in experiment
71% With sodium carbonate In 1,4-dioxane; water at 20℃; for 48 h; Boc2O (0.44 g, 2.01 mmol) was added to a solution of 3-fluoro-β-proline (1) (0.25 g, 1.90 mmol) and Na2CO3 (1 g) in 1,4-dioxane-H2O (70 mL, 1/1, v/v). After being stirred at this temperature for 30 min, the reaction mixture was stirred for an additional 48 h at room temperature. H2O (500 mL) was added and the mixture was extracted with Et2O (2 .x. 50 mL). The aqueous phase was acidified with dilute HCl to pH 3 and extracted with EtOAc (3 .x. 100 mL). After being dried (MgSO4) the solvent was evaporated to afford Boc-1 (0.31 g, 1.35 mmol, 71percent yield) as a white solid. Mp = 140-142 °C. 1H NMR (500 MHz; CDCl3; Me4Si), δ: 1.48 (9H, m, C(CH3)3), 2.45 (2H, m, 4-CH2), 3.57 (1H, m, NCHH), 3.81 (3H, m, NCHH + NCH2). 13C NMR (125 MHz; DMSO-d6; Me4Si; 2 conformers are present), δ: 28.55 (s, C(CH3)3, Boc), 34.55, 35.41 (2 d, 2JCF = 22.5 Hz, 4-CH2), 44.52, 44.78 (2 s, 5-CH2), 55.05, 55.07 (2 d, 2JCF = 23.8 Hz, 2-CH2), 79.49 (s, C(CH3)3, Boc), 98.35, 99.55 (2 d, 1JCF = 186.3 Hz, 3-CF), 153.69, 153.83 (2 s, NCO), 170.18 (d, 2JCF = 21.3 Hz, CO2H). 19F NMR (477 MHz; DMSO-d6; Me4Si; 2 conformers are present), δ: -155.61, -156.11 (2 m, F). LC-MS: 233 (M+).
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