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Synthetic method of (4S,5R)-half-ester

A synthesis method and technology of alkyl, applied in the field of synthesis of beta-half esters, can solve the problems of high price, difficult industrial production, and difficulty in catalyst preparation, and achieve easy operation, easy preparation, recyclable chemical yield and optical purity Effect

Inactive Publication Date: 2008-10-08
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the preparation of the catalyst is difficult, expensive, and not easy for industrial production

Method used

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  • Synthetic method of (4S,5R)-half-ester
  • Synthetic method of (4S,5R)-half-ester
  • Synthetic method of (4S,5R)-half-ester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Example 1: cis-1,3-dibenzyl-tetrahydro-2H-thieno[3,4-d]imidazole-2,4,6-trione (33.6g, 0.10mol), methanol (8.1 mL, 0.20mol), (1S,2S)-1-(4-nitrophenyl)-2-(N,N-dimethylamino)-3-tert-butyldimethylsilyloxy-1- Propanol (10.6g, 0.03mol) and tetrahydrofuran (200mL) were dried and placed in a reaction flask, and stirred at -15~-10°C for 36h. After the reaction was complete, the solvent was recovered under reduced pressure, cooled to room temperature, ethyl acetate (140 mL) was added to the residue and stirred for 15 min, then 5% hydrochloric acid (400 mL) was added and stirred at 10-15°C for 10 min, and the organic layer was separated. Dry over anhydrous sodium sulfate. Filtrate, and recover the solvent from the filtrate under reduced pressure, add toluene (35mol), stir for 15min, a solid is precipitated, and dried to obtain a white powder III (R=CH 3 , 35g, 95%), mp148~150℃, [α] D 22 =+2.73° (c 0.20, CHCl 3 ), IR (KBr): ν=2979, 2384, 2280, 1742, 1462, 1229, 1169, 768cm -1...

Embodiment 2

[0027] Example 2: cis-1,3-dibenzyl-tetrahydro-2H-thieno[3,4-d]imidazole-2,4,6-trione (33.6g, 0.10mol), benzyl alcohol ( 41g, 0.38mol), (1S, 2S)-1-(4-nitrophenyl)-2-(N,N-diethylamino)-3-O-trimethylsilyl-1-propanol (15.6 g, 0.05mol), tetrahydrofuran (300mL) and toluene (200mL) were placed in a dry reaction flask, and stirred at -10~-5°C for 45h. After the reaction was complete, the solvent was recovered under reduced pressure, cooled to room temperature, ethyl acetate (150 mL) was added to the residue, stirred for 10 min, then 20% acetic acid (300 mL) was added, stirred at 10-15°C for 5 min, left to stand, and the organic layer, dried over anhydrous sodium sulfate. Filtrate, recover the solvent from the filtrate under reduced pressure, add toluene (350mL), stir for 20min, a solid precipitates, and dry to obtain a white powder III (R=PhCH 2 , 37.8g, 85%), mp 57.7~60.6℃, [α] D 25 =+12.2° (c 0.20, CHCl 3 ). IR(KBr): ν=3031, 2945, 1752, 1664, 1454, 1236, 1202, 967, 741, 700cm ...

Embodiment 3

[0028] Example 3: cis-1,3-dibenzyl-tetrahydro-2H-thieno[3,4-d]imidazole-2,4,6-trione (33.6g, 0.10mol), methanol (14.2 mL, 0.35mol), (1S, 2S)-1-(4-nitrophenyl)-2-(N-methyl-N-benzyl)-3-O-tert-butyldisilyl (3.89 g, 0.01mol), carbon tetrachloride (300mL) and toluene (200mL) were placed in a dry reaction flask, and stirred at -25~-20°C for 50h. After the reaction was complete, the solvent was recovered under reduced pressure, cooled to room temperature, ethyl acetate (250 mL) was added to the residue, stirred for 5 min, then 20% sulfuric acid (300 mL) was added, stirred at 15° C. for 10 min, and the organic layer was separated. Dry over anhydrous sodium sulfate. Filtrate, the filtrate recovered the solvent under reduced pressure, added toluene (350mL), stirred for 5min, a solid precipitated, dried to obtain a white powder III (R=CH 3 , 29g, 90%), mp 147~150℃, [α] D 22 =+2.70° (c 0.20, CHCl 3 ).

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Abstract

The invention belongs organic chemistry field and in particular relates to a method to synthesize (4S,5R)- half-ester. The method takes cyclic estolide II to react with fatty alcohol and aryl-alkanol amine under the catalysis of chiral silane alkoxyl-alcohol-amine to selectively open the corresponding rings to produce (4S,5R)- half-esterI. The materials used in the method are easy to get, the reaction is mild in condition and convenient to operate, and the catalyzer can be recycled quantitatively; the yield and stereoselectivity are high, thus the method is applicable in industrial production.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and specifically relates to a method for synthesizing (4S, 5R)-half esters as shown in formula I. [0002] [0003] where R 1 is hydrogen, C 1 ~C 6 Alkyl, phenyl, p-tolyl, p-methoxyphenyl, 3,4-dimethylphenyl, 3,4-dimethoxyphenyl, 3,4,5-trimethylphenyl, 3,4,5-trimethoxyphenyl, p-chlorophenyl, Ar is phenyl, p-tolyl, p-methoxyphenyl, 3,4-dimethylphenyl, 3,4-dimethoxy phenyl, 3,4,5-trimethylphenyl, 3,4,5-trimethoxyphenyl, p-chlorophenyl, thienyl, furyl or naphthyl; R 2 for C 1 ~C 6 Alkyl, C 3 ~C 6 Cycloalkyl C 1 ~C 6 Alkyl, C 2 ~C 6 alkenyl, aryl C 1 ~C 6 Alkyl or aryl C 2 ~C 6 Alkenyl. Background technique [0004] It is known that (4S,5R)-half-ester represented by formula I is a key intermediate in the synthesis of (+)-biotin ((+)-Biotin). [0005] The synthesis of I was first reported by Gerecke et al. (Helv Chim Acta, 1970, 53, 991), using cyclic anhydride II and cyclohexanol...

Claims

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Application Information

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IPC IPC(8): C07D233/32C07B53/00B01J31/02
CPCY02P20/584
Inventor 陈芬儿戴惠芳盛浩赵磊
Owner FUDAN UNIV
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