醚[6]。在Boc脱去过程中TBDPS[7]和TBDMS[8]基对CF3COOH是稳定的（在TBS存在，用相对稀一些的10－20 ％TFA）。伯胺衍生物存在下，ZnBr2/CH2Cl2可以选择性的脱除仲胺上的Boc[9]。

1. F. Cavelier, C. Enjabal., Tetrahedron Lett., 1996, 37, 5131

2. F. S. Gibson, S. C. Bergmeier, H. Rapoport., J. Org. Chem., 1994, 59, 3216 3. A.Nudelman, Y. Bechor et al., Synth. Commun., 1998, 28, 471

4. R. S. Lott, V. S. Chauhan et al., J. Chem. Soc. Chem. Commun., 1979, 495; G. A. Olah, S. C. Narang., Tetrahedron., 1982, 38, 2225

5. R. A. T. M. van Benthem, H. Hiemstra et al., J. Org. Chem., 1992, 57, 6083

6. M. Bodanszky, A. Bodanszky., Int. J. Pept. Protein Res., 1984, 23, 565; Y. Masui, N. Chino et al., Bull. Chem. Soc. Jpn., 1980, 53, 464

7. P. A. Jacobi, S. Murphree et al., J. Org. Chem., 1996, 61, 2413 8. J. Deng, Y. Hamada et al., J. Am. Chem. Soc., 1995, 117, 7824 9. S. C. Nigam, A. Mann et al., Synth. Commun., 1989, 19, 3139

2.2.2.1.1 TMSOTf中性条件下脱Boc示例

ONBocHNOHOTBDMSOTfCH2Cl2H2NOTBDMSN

Gilbertson, Scott R; Chang, Cheng-Wei et al., J. Org. Chem., 1998, 63(23), 8424-8431 To a solution containing 2 (1.0 g, 3.9 mmol) in 30 mL of dry CH2Cl2 was slowly added TBDMSOTf (0.9 mL, 4.1 mmol). After stirring the reaction mixture for 6 h, the solvent was evaporated, and the crude product (0.8 g, 75%) was obtaineded, which was used directly in the next step.

2.2.2.1.2 TMSOTf-2,6-lutidine中性条件下脱Boc示例1

BocHNOOOSOTBDMSOTf2,6-LutidineCH2Cl2OOOSOH2N Kemp, Scott J; Bao, Jiaming et al J. Org. Chem., 1996, 61(20), 7162-7167

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To a stirring solution of compound 1 (800 mg, 2.0 mmol) and 2,6-lutidine (0.4463 ml, 4.0 mmol) in CH2Cl2 (6 mL) was added tert-butyldimethylsilyl triflate (0.690 ml, 3.0 mmol) dropwise over 5 min. After 20 min, saturated NH4Cl (10 mL) was added. The mixture was stirred and separated, and the aqueous layer was extracted with Et2O (3 x 15 mL). The combined organic layers were washed with water (2 x 10 mL) and saturated NaCl (10 mL), dried (MgSO4), and concentrated to give the crude silyl carbamate, which was dissolved in THF (10 mL) and cooled to 0°C. A 1.0 M solution of TBAF in THF (2 mL, 2 mmol) was added over 5 min, and then the solution was stirred at 0°C for 1 h. The solution was concentrated and chromatographed (95:5 CH2Cl2-methanol) through a small plug of silica to give compound 2 (882 mg, 75%) as a clear oil.

2.2.2.1.3 TMSOTf-2,6-lutidine 条件下脱Boc示例2

OHNOO1OOTBDMSOTfO2,6-LutidineCH2Cl2OOHNH2N2OOBocHN

Sakaitani, Masahiro; Ohfune, Yasufumi; J. Org. Chem., 1990, 55(3), 870-876

To a stirred solution of compound l (500 mg, 1.52 mmol) and 2,6-lutidine (0.353 ml, 3.04 mmol) in dry CH2C12 (3.0 mL) at 0 \t-BuMe2SiOTf (0.523 ml, 2.28 mmol). The reaction mixture was stirred at 0°C for 15 min, quenched with saturated aqueous ammonium chloride solution, and extracted with ether several times. The combined organic phase was washed with H2O and then brine, dried (MgSO4), and concentrated in vacuo to give an oily residue, which upon purification by column chromatography on silica gel (elution with 50% ether in hexane) gave O-silyl ester compound 2 (652 mg, 97%): colorless needles; mp 64.0-65.0°C (hexane).

2.2.2.2 TFA脱Boc示例

TBSONHBocCOOMeTFACH2Cl2TBSONH2COOMeCbzNCbzN

M. Alberto; A. Eduardo et al., J. Org. Chem., 2004, 21, 7004

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To a solution of the β-aminoester (0.2 mmol) in CH2Cl2 (3 mL), cooled to 0°C was added TFA (1mL). After the consumption of the starting material (45 min, monitored by TLC), the mixture was evaporated and then saturated aqueous NaHCO3 was added. The aqueous layer was extracted twice with CH2Cl2 (15 mL), and the organic layer washed with brine and dried over anhydrous Na2SO4. The solvent was removered under vacuum, to afford the amine, which were employed without further purification to prepare the Mosher’s diastereoisomeric amides.

2.2.2.3 HCl-Et2O脱Boc示例

ONHBocOOHClEt2OHOOCClH.HNO

C. Mühlemann, P. Hartmann, J. P. Obrecht., Org. Syn., 71, 200

tert-Butyl [1-(tert-butoxycarbonyl)-3-oxo-4-pentenyl]carbamate, 8.73 g (0.0308 mol), is dissolved in 280 mL of an ice-cooled, saturated solution of hydrogen chloride in ether. The solution is kept without stirring at room temperature overnight. The resulting suspension is filtered and the filter cake is immediately washed with dry ether. The washing with ether is repeated four times and, after drying under reduced pressure, 5.48 g (99%) of 4-ketopipecolic acid hydrochloride is obtained as a colorless powder, mp 139–142°C dec.

2.2.2.4 HCl-THF脱Boc示例

OHNHCOOt-BuBocHNH2N HClTHFH2NOHNHCOOHH

J. Wehbe et al., Tetrahedron: Asymmetry, 2004, 15, 851

To the Boc protected amine (0.06 g, 0.17 mmol) dissolved in THF (1mL) was added 2M HCl (1mL, 2 mmol) and the mixture stirred 2 h at room temperature. After evaporation of the solvent, the product was extracted into EtOAc (3. 5mL). The organic layer was dried and evaporated under vacuum to afford 17b in 95% yield as a white solid.

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2.2.2.5.1 叔丁酯存在下的脱Boc示例1

OO1Me3SiICHCl3ONH2OOONBoc

US5610144

1.77 ml of Me3SiI are added dropwise at room temperature in the vicinity of 25°C to a soution of 3.8 g of compound 1 in 50 ml of CHCl3. Stirring is contiuned for 30 min, then 20 ml f water are added. The aqueous phase is separated, then extracted with CHCl3(2 x 20 ml). The organic phases are combined, washed successively with a saturated aqueous Na2CO3(30 ml) and water(2 x 30 ml), then dried over MgSO4 and concentrated to dryness under reduced pressure at 40°C. The mixture of the two diastereoisomers obtained is separated by chromatography on silica (eluent: ethyl acetate/cyclohexane = 1/4). The fractions containing the expected product are combined and concentrated to dryness under reduced pressure at 40°C to give compound 2 (0.5 g), as a yellow-orange oil, used as it is in subsequent syntheses.

2.2.2.5.2 叔丁酯存在下的脱Boc示例1

ONOO1Boc1.1 M HClEtOAcNHOO2O

US2002045623

To asolution of compound 1 (6.3 g, 21.0 mmol) in ethyl acetate (50 ml) was added 1.1 M HCl in ethyl acetate (28.7 ml, 31.5 mmol). The reaction was stirred at room temperature for 1 h, then washed with water, saturated aq. NaHCO3 and brine. The organic phase was dried (MgSO4), filtered and evaporated to afford compound 2 (3.11 g, 74%) as a yellow oil which crystallized upon standing.

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