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BOC保护方法

1. Single Step

63%

Overview

Steps/Stages Notes

1.1S:H2O, S:Dioxane, 0°C; 15 min, 0°C

1.2R:NaOH, 0°C → rt, pH 10.5; 2 h, rt

Reactants: 2, Reagents: 1, Solvents: 2, Steps:

1, Stages: 2, Most stages in any one step: 2

References

Synthesis of N-propynyl analogues of peptide

nucleic acid (PNA) monomers and their use in

the click reaction to prepare N-functionalized

PNAs

By Howarth, Nicola M. and Ricci, Jennyfer

From Tetrahedron, 67(49), 9588-9594; 2011 CASREACT ?: Copyright ? 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.

2. Single Step

91%

Overview

Steps/Stages Notes

1.1R:HCl, 1-3 d, rt HCl gas used, Reactants: 2, Reagents: 1,

Steps: 1, Stages: 1, Most stages in any one

step: 1

References

Combinatorial synthesis of 3,5-dimethylene

substituted 1,2,4-triazoles

By Woodard, Scott S. and Jerome, Kevin D.

From Combinatorial Chemistry & High

Throughput Screening, 14(2), 132-137; 2011 CASREACT ?: Copyright ? 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.

3. Single Step

Overview

Steps/Stages Notes

1.1R:Et3N, S:MeCN, 5 min, rt

1.2C:4-DMAP, S:MeCN, 16 h, rt

Reactants: 2, Reagents: 1, Catalysts: 1,

Solvents: 1, Steps: 1, Stages: 2, Most stages

in any one step: 2

References

Preparation of sulfonylaminomethyl five-

membered heterocyclic carboxamide

derivatives as bradykinin B1 antagonists and

their preparation, pharmaceutical

compositions and use in the treatment of

inflammatory-related disorders

By Madden, James et al

From PCT Int. Appl., 2010020556, 25 Feb

2010

Experimental Procedure

Ethyl [(tert-butoxycarbonyl)amino]acetate. Int 287. Ethyl Chloroformate (2.7 mL, 28.5 mmol) in MeCN

(5 mL) was added to a solution of Boc glycine (5.0 g, 28.5 mmol) and TEA (3.9 mL, 28.5 mmol) in

MeCN (15 mL) under N2. After 5 minute a solution of DMAP (1.7 g, 14.25 mmol) in MeCN (14 mL) was

added and the resultant yellow solution was stirred at ambient temperature for 16 h. The pale yellow

suspension was concentrated in vacuo and the residue diluted with DCM (100 mL) and washed with

saturated aqueous NaHCO3 (50 mL) and aqueous HCl (0.1 M, 50 mL). The organics were dried over

MgSO4 and concentrated in vacuo to a pale yellow oil which was used without further purification.

Yield: 6.6 g. 1H NMR (500 MHz, CDCl3) δ ppm 4.95 - 5.09 (1 H, m), 4.22 - 4.23 (1 H, m), 4.20 (2 H, q J

7.2 Hz), 3.86 - 3.93 (2 H, m), 1.46 (9 H, s), 1.28 (2 H, t,J 7.2 Hz).

CASREACT ?: Copyright ? 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.

4. Single Step

Overview

Steps/Stages Notes

1.1 -no experimental detail, ethanol reactant

assumed, Reactants: 2, Steps: 1, Stages: 1,

Most stages in any one step: 1

References

Synthesis and biological activity of dipeptides

containing S-hexylcysteine

By Bruzgo, Irena and Midura-Nowaczek,

Krystyna

From Acta Poloniae Pharmaceutica, 64(5),

479-482; 2007

5. Single Step

82%

Overview

Steps/Stages Notes

1.1C:7787-58-8, S:MeCN, 0.5 h, rt

1.2C:H2O, 2 h, rt

1.3R:NaHCO3, S:H2O, rt

chemoselective, Reactants: 1, Reagents: 1,

Catalysts: 2, Solvents: 2, Steps: 1, Stages: 3,

Most stages in any one step: 3

References

Efficient and selective cleavage of the t-

butoxycarbonyl group from di-t-

butylimidodicarbonate using catalytic

bismuth(III) bromide in acetonitrile

By Zheng, Jianlong et al

From Tetrahedron Letters, 50(36), 5094-

5097; 2009

6. Single Step

100%

Overview

Steps/Stages Notes

1.1R:Et3N, S:THF, 0°C; 0°C → rt; 18 h, rt; 3 h, rt → 50°C Reactants: 2, Reagents: 1, Solvents: 1, Steps:

1, Stages: 1, Most stages in any one step: 1

References

Palladium-catalysed enantioselective α-

hydroxylation of β-ketoesters

By Smith, Alexander M. R. et al

From Chemical Communications (Cambridge,

United Kingdom), (26), 3925-3927; 2009

7. Single Step

99%

Overview

Steps/Stages Notes

1.1rt; 5 min, rt Reactants: 2, Steps: 1, Stages: 1, Most stages

in any one step: 1

References

Environmentally benign N-Boc protection

under solvent- and catalyst-free conditions

By Jia, Xueshun et al

From Synlett, (5), 806-808; 2007 CASREACT ?: Copyright ? 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.

8. Single Step

75%

Overview

Steps/Stages Notes

1.1C:4420-74-0 silica-bound, S:CH2Cl2, S:MeCN, 30 min, rt chemoselective, solid-supported catalyst,

Reactants: 2, Catalysts: 1, Solvents: 2, Steps:

1, Stages: 1, Most stages in any one step: 1

References

Studies in novel synthetic methodologies.

Part 91. A highly chemoselective Boc

protection of amines using sulfonic-acid-

functionalized silica as an efficient

heterogeneous recyclable catalyst

By Das, Biswanath et al

From Tetrahedron Letters, 47(43), 7551-

7556; 2006

9. Single Step

99%

Overview

Steps/Stages Notes

1.1R:NaHCO3, S:MeCN, 0°C; 0°C → rt; 16 h, rt Reactants: 2, Reagents: 1, Solvents: 1, Steps:

1, Stages: 1, Most stages in any one step: 1

References

Glycosylated Foldamers To Probe the

Carbohydrate-Carbohydrate Interaction

By Simpson, Graham L. et al

From Journal of the American Chemical

Society, 128(33), 10638-10639; 2006 Experimental Procedure

Di-tert-butyl dicarbonate (3.13 g, 14.3 mmol) was added to a cooled (0 °C), stirred suspension of

glycine ethyl ester hydrochloride salt (2.0 g, 14.3 mmol) and sodium hydrogen carbonate (3.61 g, 42.9

mmol) in acetonitrile (68 mL). The resultant mixture was warmed to room temperature and stirred for

16 hours under nitrogen. The reaction mixture was concentrated under vacuum and the resulting

residue partitioned between CH2Cl2 (70 mL) and water (70 mL). The organic layer was separated and

the remaining aqueous phase extracted with CH2Cl2 (2 x 70 mL). All organics were combined, washed

with water (70 mL), dried over Na2SO4 and concentrated under vacuum to afford the title compound

(2.91 g, 99%) as a colorless oil;. R f 0.52 (1:1 EtOAc/hexane); 1H NMR (270 MHz, CDCl3) δH 1.28 (3H,

t, J= 7.0, CH2C H3), 1.46 (9H, s, C(C H3)3), 3.90 (2H, d, J= 5.5, COC H2NH), 4.21 (2H, q, J= 7.0

C H2CH3), 5.01 (1H, br m, CH2N H); 13C NMR (67.9 MHz, CDCl3) δC 14.2 (C H3CH2), 28.3 (C(C H3)3,

42.5 (C H2NH), 61.3 (C H2CH3), 80.0 (C(CH3)3), 155.7 (C ONH), 170.4 (C OOCH2).

10. Single Step

93%

Overview

Steps/Stages Notes

1.1R:Et3N, C:4-DMAP, S:MeCN, 5 min, 0°C; overnight, rt using a borosilicate glass micro reactor with

electroosmotic flow gave similar conversion,

Reactants: 2, Reagents: 1, Catalysts: 1,

Solvents: 1, Steps: 1, Stages: 1, Most stages

in any one step: 1

References

Solution phase synthesis of esters within a

micro reactor

By Wiles, Charlotte et al

From Tetrahedron, 59(51), 10173-10179;

2003

11. Single Step

98%

Overview

Steps/Stages Notes

1.1R:Et3N, S:THF, 36 h Reactants: 2, Reagents: 1, Solvents: 1, Steps:

1, Stages: 1, Most stages in any one step: 1

References

Large scale synthesis of 1,2,4- and 1,3,4-

oxadiazole carboxylates

By Kolb, Hartmuth C. et al

From U.S. Pat. Appl. Publ., 20040019215, 29

Jan 2004

Experimental Procedure

1. Ethyl 2-[(tert-butoxy)carbonylamino]acetate (5) Di-tert-butyl dicarbonate (365 g, 1.67 mol) in

tetrahydrofuran (1L) is added dropwise to a 0°C. solution of glycine ethyl ester hydrochloride (232.5 g,

1.66 mol) and triethylamine (497.5 ml, 3.57 mol) in tetrahydrofuran (

2.5 L.) The reaction mixture is

vigorously stirred for 36 hours and then filtered. The filtrate is the concentrated in vacuo to afford 329.4

9 (98%) of compound 5 as a white solid. Ethyl 2-[(tert-butoxy)carbonylamino]acetate (5), yield 329.4 9

(98%)

12. Single Step

43%

Overview

Steps/Stages Notes

1.1R:Et3N, R:EtOH, S:MeCN, 80°C 1.2 2 h, 80°C Reactants: 2, Reagents: 2, Solvents: 1, Steps: 1, Stages: 2, Most stages in any one step: 2 References

Synthesis of ethyl esters of N-substituted amino acids using 3-

(ethoxycarbonyl)benzotriazole 1-oxide

By Topuzyan, V. O. et al

From Hayastani Kimiakan Handes, 55(3), 95-102; 2002

13. Single Step

85%

Overview

Steps/Stages Notes

1.1R:Disodium carbonate, S:EtOH

1.2 -

Reactants: 2, Reagents: 1, Solvents: 1, Steps:

1, Stages: 2, Most stages in any one step: 2

References

Process for producing N-(alkoxycarbonyl)-N-

(cyanoethyl)amino acid alkyl esters

By Hirano, Naoki and Iwasaki, Fumiaki

From Eur. Pat. Appl., 1000931, 17 May 2000 Experimental Procedure

A hundred milliliters of ethanol and 27.92 g (0.2 mol) of glycine ethyl ester hydrochloride were injected

into a 300-ml four-necked flask equipped with a stirrer and a thermometer, and 11.66 g (0.11 mol) of

sodium carbonate was further added at room temperature while the above mixture was stirred. The

resulting mixture was stirred for 30 minutes. Thereafter, 12.74 g (0.24 mol) of acrylonitrile was added,

and the resulting mixture was allowed to react at 50 to 60°C for 6 hours. After the end of the reaction,

the reaction suspension was filtered, and the filtrate was concentrated under reduced pressure.

Thereafter, the residue was distilled under reduced pressure to obtain 43.3 g of N-cyanoethyl glycine

ethyl ester. The yield was 84.6 %. N-cyanoethyl glycine ethyl ester, yield 43.3 g 84.6 %.

14. Single Step

97%

Overview

Steps/Stages Notes

1.1C:54761-04-5 silica-supported, S:CH2Cl2Reactants: 1, Catalysts: 1, Solvents: 1, Steps:

1, Stages: 1, Most stages in any one step: 1

References

A facile new method for selective deprotection

of N-(tert-butoxycarbonyl)-protected

carboxamides with Yb(OTf)3 supported on

silica gel

By Kotsuki, Hiyoshizo et al

From Tetrahedron Letters, 39(27), 4869-

4870; 1998

15. Single Step

81%

Overview

Steps/Stages Notes

1.1R:EtOH, R:HCl

1.2R:NaOH, S:H2O

1.3 -

Reactants: 2, Reagents: 3, Solvents: 1, Steps:

1, Stages: 3, Most stages in any one step: 3

References

Preparation of N-(alkoxycarbonyl)amino acid

esters

By Sugita, Juzo et al

From Jpn. Kokai Tokkyo Koho, 07101928, 18

Apr 1995

16. Single Step

82%

Overview

Steps/Stages Notes

1.1R:EDTA ?4 Na, C:9001-73-4, S:CH2Cl2citrate-phosphate buffer, pH 4.2, Reactants: 2,

Reagents: 1, Catalysts: 1, Solvents: 1, Steps:

1, Stages: 1, Most stages in any one step: 1

References

Synthesis of amino acid esters by papain

By Cantacuzene, D. et al

From Tetrahedron, 43(8), 1823-6; 1987 CASREACT ?: Copyright ? 2013 American Chemical Society. All Rights Reserved. CASREACT contains reactions from CAS and from: ZIC/VINITI database (1974-1999) provided by InfoChem; INPI data prior to 1986; Biotransformations database compiled under the direction of Professor Dr. Klaus Kieslich; organic reactions, portions copyright 1996-2006 John Wiley & Sons, Ltd., John Wiley and Sons, Inc., Organic Reactions Inc., and Organic Syntheses Inc. Reproduced under license. All Rights Reserved.

BOC保护方法

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