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Method for preparing and removing saccharide hydroxyl protecting group dimethyl phenylacetyl DMNA

A technology of dimethyl phenylacetyl and sugar hydroxyl, applied in the field of chemistry, can solve the problem that the protective group cannot have good compatibility, and achieve the effects of good stereoselectivity, wide application range and easy operation.

Inactive Publication Date: 2017-06-13
JIANGXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, Piv is too stable under many conditions, and the conditions for its removal are often severe. In order to make it more convenient to remove, in 1998, Crimmins et al. developed a similar 2,2-dimethyl-4-pentenoyl Hydroxyl protecting group, which is removed by intramolecular ring-closing reaction to expose the required hydroxyl [Crimmins.T.M.et al.Tetrahedron Lett.1998,39,7005], in 1999, Trost et al. synthesized (+)-Cyclophellitol At the same time, a protective group similar to Piv with carbon chain extension was also used, which can also remove the silicon group under the action of HF / Py, and then undergo an intramolecular ring closure reaction to remove [Trost, B.M.et al. Tetrahedron Lett.1999,40,219], but the removal of the above-mentioned protecting groups needs to generate the exposed hydroxyl group at the γ position under acidic or alkaline conditions, and then carry out intramolecular cyclization and removal. Under this condition, the intramolecular Some acid- or base-sensitive protecting groups that may exist may not have good compatibility

Method used

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  • Method for preparing and removing saccharide hydroxyl protecting group dimethyl phenylacetyl DMNA
  • Method for preparing and removing saccharide hydroxyl protecting group dimethyl phenylacetyl DMNA
  • Method for preparing and removing saccharide hydroxyl protecting group dimethyl phenylacetyl DMNA

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Methyl 2,3,4-tri-O-benzoyl-6-O-(2,2-dimethyl-2-(o-nitrophenyl)acetyl)-α-D-glucopyranose Glycoside preparation,

[0018]

[0019] Step 1: Preparation of the protecting group 2,2-dimethyl-(2'-nitro)phenylacetyl (DMNA), under ice bath, dissolve 10g o-nitrophenylacetic acid in 200mL methanol solution, then slowly add 30mL Thionyl chloride was reacted in an ice bath for 30 minutes. After the reaction was monitored by TLC, the crude product was concentrated under reduced pressure, and 10 g of methyl o-nitrophenylacetate was obtained by column chromatography, with a yield of 93%;

[0020] Dissolve 10 g of the product obtained above in 100 mL of N,N-dimethylformamide, slowly add 6.15 g of sodium hydride in an ice bath, slowly add 9.8 mL of methyl iodide, and slowly raise the reaction system to room temperature, react for 12 hours, TLC After monitoring the completion of the reaction, the reaction system was diluted with ethyl acetate, washed with water, washed with saturated...

Embodiment 2

[0030] Methyl 2,3,4-tri-O-benzyl-6-O-(2,2-dimethyl-2-(o-nitrophenyl)acetyl)-α-D-glucopyranoside the preparation of

[0031] Step 1: The synthetic method is as shown in Step 1 of Example 1;

[0032] Step 2: introduction of novel protecting group 2,2-dimethyl-(2'-nitro)phenylacetyl (DMNA),

[0033]

[0034] Synthetic method is as shown in the step 2 of embodiment 1, (productive rate 87%), [α] D 25 =+21.5(c 1.00, CHCl 3 ); 1 HNMR (400MHz, CDCl 3 )δ7.90 (d, J = 8.0Hz, 1H), 7.58 (d, J = 4.0Hz, 2H), 7.39-7.24 (m, 16H), 4.96 (d, J = 10.8Hz, 1H), 4.80- 4.75(m,3H),4.66(d,J=12.0Hz,1H),4.55(d,J=3.6Hz,1H),4.47-4.42(m,2H),4.14(dd,J=6.0,12.0Hz ,1H),3.97(t,J=9.2Hz,1H),3.77-3.72(m,1H),3.44(dd,J=3.2,9.6Hz,1H),3.29(dd,J=8.8,10.4Hz, 1H), 3.21(s,3H), 1.67(s,3H), 1.66(s,3H); 13 C NMR (100MHz, CDCl 3 )δ175.0, 148.6, 139.2, 138.6, 138.1, 137.9, 133.2, 128.4(2C), 128.0(2C), 127.9, 127.8, 127.7(2C), 125.6, 97.7, 81.9, 79.9, 78.1, 75.8, 75.1, 73.3 68.6, 63.7, 54.9, 46.6, 27.2; HRMS (ESI) ...

Embodiment 3

[0039] Preparation of 2,3,6-tri-O-benzyl-4-O-(2,2-dimethyl-2-(o-nitrophenyl)acetyl)-α-D-glucopyranoside ,

[0040] Step 1: The synthetic method is as shown in Step 1 of Example 1;

[0041] Step 2: introduction of novel protecting group 2,2-dimethyl-(2'-nitro)phenylacetyl (DMNA),

[0042]

[0043] Synthetic method is as shown in the step 2 of embodiment 1, (productive rate 90%), [α] D 25 =+61.0 (c 0.84, CHCl 3 ); 1 HNMR (400MHz, CDCl 3 )δ7.83(dd, J=1.2,8.4Hz,1H),7.55(td,J=1.2,8.0Hz,1H),7.48(dd,J=1.6,8.0Hz,1H),7.40-7.36(m ,3H),7.32-7.22(m,13H),5.04(t,J=9.6Hz,1H),4.97(d,J=11.6Hz,1H),4.68-4.62(m,3H),4.56-4.49( m,3H),3.92(t,J=9.2Hz,1H),3.83-3.78(m,1H),3.71(dd,J=1.6,10.8Hz,1H),3.63-3.57(m,2H),3.39 (s,3H),1.55(s,3H),1.52(s,3H); 13 C NMR (100MHz, CDCl 3 )δ174.3,148.8,138.7,138.6,138.4,137.8,133.0,128.4,128.2,128.1(2C),127.9(2C),127.8,127.4,127.1,126.9,125.5,97.6,79.8,78.9,34.3,7 , 71.2, 69.1, 69.0, 55.4, 46.9, 27.1, 27.0; HRMS (ESI) calcd for C38H41NO9Na[M+Na]+678.2673 f...

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Abstract

The invention relates to a method for preparing and removing saccharide hydroxyl protecting group dimethyl phenylacetyl DMNA. The method comprises the following steps: (1) efficiently introducing saccharide hydroxyl protecting group dimethyl phenylacetyl into saccharide hydroxyl; and (2) efficiently removing a hydroxyl protecting group shown in the description. The method is environmentally friendly and has the advantages that the advantages that the preparation is simple, the introduction is efficient, the operation is easy, the removal is efficient, and the application range is wide; and furthermore, a protecting group has very good stereoselectivity when being used for protecting 2-hydroxyl of a glycosyl donor, so that the development and application of the protecting group are promoted.

Description

technical field [0001] The invention relates to the field of chemistry, in particular to a method for preparing and removing sugar hydroxyl protecting group dimethylphenylacetyl DMNA. Background technique [0002] Sugar, also known as carbohydrate, together with protein, nucleic acid and lipid, is called four important biological macromolecules in the process of life activities. Sugar is an important molecule in the living body, and it participates in living organisms, especially multicellular organisms fertilization, implantation, differentiation, development, immunity, infection, canceration, aging and other time and space processes, and is closely related to a variety of diseases, however, there are usually multiple reactive sites with similar reactivity in monosaccharide molecules , we often only want one of the active sites to remain active, and the other sites must be selectively protected from participating in the reaction, or protected by special protecting groups to...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C201/12C07C205/56C07H15/04C07H15/18C07H9/04C07H23/00C07H1/00
CPCY02P20/55C07C201/12C07H1/00C07H9/04C07H15/04C07H15/18C07H23/00C07C205/56
Inventor 孙建松刘慧廖进喜
Owner JIANGXI NORMAL UNIV