Method for synthesizing multi-substituted silicon-based allene in highly selective way

A silicon-based allene and multi-substitution technology, which is applied in the field of synthesizing multi-substituted silicon-based allenes, can solve the problems of expensive environment, unfriendliness, and poor functional group compatibility, and achieve good functional group compatibility, easy separation and purification, and mild conditions Effect

Inactive Publication Date: 2014-03-05
ZHEJIANG UNIV
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Problems solved by technology

The silicon-based allene compounds reported in the past are mainly prepared by adding equivalent metal reagents at low temperature (Tetrahedron: Asymmetry, 2008, 19, 2882; Org. Lett., 2009 , 11, 3614.) or use equivalent expensive and environmentally unfriendly heavy metals t

Method used

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  • Method for synthesizing multi-substituted silicon-based allene in highly selective way
  • Method for synthesizing multi-substituted silicon-based allene in highly selective way

Examples

Experimental program
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Effect test

Embodiment 1

[0018] Add to the reaction tube N -Methoxybenzamide (151.7 mg, 1 mmol), pentamethylcyclopentadienyl rhodium dichloride dimer (12.4 mg, 0.02 mmol), sodium acetate (25 mg, 0.3 mmol), 3- Trimethylsilyl-1,2-heptadiene (25 mg, 0.3 mmol), methanol (6 mL), water (0.3 mL), stirred at room temperature, and reacted for 11 h. Filter the short column with ether, concentrate, and obtain by flash column chromatography. 261.1 mg of 2-(3-trimethylsilyl-1,2-heptadien-1-yl)benzamide was obtained as a solid, with a yield of 91%.

[0019] Melting point 93.2-94.4 o C (hexane / ethyl acetate); 1 H NMR (300 MHz, CDCl 3 ) δ 7.51 (t, J = 7.7 Hz, 2 H, Ar-H), 7.37 (t, J = 7.7 Hz, 1 H, Ar-H), 7.27 (brs, 1 H, one proton of NH 2 ), 7.16 (t, J = 7.4 Hz, 1 H, Ar-H), 6.52 (t, J = 2.9 Hz, 1 H, CH=), 6.16 (brs, 1 H, one proton of NH 2 ), 2.27-2.03 (m, 2 H, CH 2 ), 1.66-1.24 (m, 4 H, CH 2 × 2), 0.93 (t, J = 7.2 Hz, 3 H, CH 3 ), 0.20 (s, 9 H, TMS); 13 C NMR (75 MHz, CDCl 3 ) δ 205.5, 172.4, 1...

Embodiment 2

[0021] By the method described in Example 1, the difference is that the substrate and reagent used are: 4-chloro- N -Methoxybenzamide (1.8570g, 10 mmol), pentamethylcyclopentadienyl rhodium dichloride dimer (124.2 mg, 0.2 mmol), sodium acetate (246.7 mg, 3 mmol), 3- Trimethylsilyl-1,2-heptadiene (1.6789 g, 10 mmol), methanol (60 mL), water (3 mL), reacted at room temperature for 16 h to give the product 4-chloro-2-(3-tri Methylsilyl-1,2-heptadien-1-yl)benzamide 2.5643 g, solid, yield 80%.

[0022] Melting point 85.6-85.9 o C (hexane / ethyl acetate); 1 H NMR (300 MHz, CDCl 3 ) δ 7.46-7.34 (m, 2 H, Ar-H), 7.10 (dd, J 1 = 8.4 Hz, J 2 = 1.5 Hz, 1 H, Ar-H), 6.75 (brs, 1 H, one proton of NH 2 ), 6.40 (t, J = 1.8 Hz, 1 H, CH=), 5.96 (brs, 1 H, one proton of NH 2 ), 2.26-2.01 (m, 2 H, CH 2 ), 1.62-1.22 (m, 4 H, CH 2 × 2), 0.89 (t, J = 7.2 Hz, 3 H, CH 3 ), 0.16 (s, 9 H, TMS); 13 C NMR (75 MHz, CDCl 3 ) δ 205.2, 171.4, 136.7, 136.3, 130.7, 129.1, 126.4, 125.5, 101.5...

Embodiment 3

[0024] According to the method described in Example 1, the difference is that the substrate and reagent used are: 4-methoxycarbonyl- N -Methoxybenzamide (209.5 mg, 1 mmol), pentamethylcyclopentadienyl rhodium dichloride dimer (12.6 mg, 0.02 mmol), sodium acetate (25.5 mg, 0.3 mmol), 3- Trimethylsilyl-1,2-heptadiene (168.2 mg, 1 mmol), methanol (6 mL), water (0.3 mL), reacted at room temperature for 14 h to give the product 4-methoxycarbonyl-2-(3 - Trimethylsilyl-1,2-heptadien-1-yl) benzamide 297.4 mg, liquid, yield 86%.

[0025] 1 H NMR (300 MHz, CDCl 3 ) δ 8.14 (d, J = 1.2 Hz, 1 H, Ar-H), 7.77 (dd, J 1 = 8.1 Hz, J 2 = 1.2 Hz, 1 H, Ar-H), 7.51 (d, J = 7.8 Hz, 1 H, Ar-H), 6.51 (brs, 1 H, one proton of NH 2 ), 6.39 (t, J = 2.9 Hz, 1 H, CH=), 5.97 (brs, 1 H, one proton of NH 2 ), 3.92 (s, 3 H, OCH 3 ), 2.27-2.01 (m, 2 H, CH 2 ), 1.62-1.22 (m, 4 H, CH 2 × 2), 0.88 (t, J = 7.2 Hz, 3 H, CH 3 ), 0.18 (s, 9 H, TMS); 13 C NMR (75 MHz, CDCl 3 ) δ 205.5, 171.1, ...

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Abstract

The invention relates to a method for synthesizing multi-substituted silicon-based allene, namely a method for synthesizing multi-substituted silicon-based allene in a highly regioselective and stereoselective way by reacting N-methoxybenzamide compounds with silicon-based allene. The method is simple to operate, raw materials and reagents are easy to obtain, the reaction has high regioselectivity and stereoselectivity, functional group compatibility is good, multiple substituent groups can be introduced simultaneously, products are easy to separate and purify, and the method is applicable for synthesizing various multi-substituted silicon-based compounds.

Description

technical field [0001] The present invention relates to a method for synthesizing multi-substituted silyl allenes, namely by N -Reaction of methoxybenzamide compounds with silyl allenes, a method for synthesizing polysubstituted silyl allenes with high regioselectivity and stereoselectivity. [0002] Background technique [0003] Silicon-based allene compounds are one of the very important intermediates in organic synthesis. They can react with various reagents such as aldehydes, ketones, α-β unsaturated aldehydes and ketones, acetals and halides to obtain alcohols, furans, Alkynes and many other useful compounds. ( Org. React 1989, 35 , 501; Eur. J. Org. Chem. 2013, 148.). The silicon-based allene compounds reported in the literature in the past are mainly obtained by adding equivalent metal reagents ( Tetrahedron: Asymmetry , 2008, 19, 2882; Org. Lett. , 2009, 11, 3614.) or use equivalent expensive and environmentally unfriendly heavy metals to participate in th...

Claims

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Application Information

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IPC IPC(8): C07F7/10C07F7/12
Inventor 麻生明曾荣吴尚泽傅春玲
Owner ZHEJIANG UNIV
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