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Practical novel method for nonmetal-catalyzed silicon disprotection

A non-metallic catalysis and deprotection technology, used in chemical instruments and methods, organic chemistry, hydrocarbons, etc., can solve problems such as unreported

Active Publication Date: 2017-12-12
TAIZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] Compared with the above-mentioned traditional or expensive metal-catalyzed silicon-based deprotection methods with poor atom economy, the cheap and easy-to-obtain inorganic base-catalyzed method obviously has the advantages of convenient operation, low production cost, and high industrial application value. None have been reported so far

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  • Practical novel method for nonmetal-catalyzed silicon disprotection
  • Practical novel method for nonmetal-catalyzed silicon disprotection

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Add trimethylphenylsilane (1 mmol), inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsilanolate (sodium) (0.05 mmol), 2 mL DMA or DMSO solvent to 10 mL In the sealed tube, heat and stir in an oil bath at 60°C for 6.5 hours, and track the reaction progress according to TLC. After the reaction is completed, add an equivalent amount of mesitylene or n-undecane to the crude product as an internal standard to measure by GC and GC-MS The exact yield of the product. According to GC and GC-MS, when using DMSO as reaction solvent, inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or trimethylsiliconate potassium (sodium) as catalyst, the yield of product is successively : 80%, 74%, 79%, 84%, 95%, 92%. When using DMA as the reaction solvent, the inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsiliconate (sodium) is used as the catalyst, and the...

Embodiment 2

[0020] 4-Methyltrimethylphenylsilane (1 mmol), inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsilanolate (sodium) (0.05 mmol), 2 mL DMA or DMSO solvent Add them to 10mL sealed tubes one by one, heat and stir in an oil bath at 60°C for 8 hours, and track the reaction progress according to TLC. GC-MS determined the exact yield of the product. According to GC and GC-MS, when using DMSO as reaction solvent, inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or trimethylsiliconate potassium (sodium) as catalyst, the yield of product is successively : 61%, 59%, 77%, 69%, 97%, 90%. When using DMA as reaction solvent, inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsiliconate (sodium) are as catalyst, and the yield of product is successively: 47%, 55%, 59%, 49%, 92%, 91%.

Embodiment 3

[0022] 3-Methyltrimethylphenylsilane (1 mmol), inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsilanolate (sodium) (0.05 mmol), 2 mL DMA or DMSO solvent Add them to 10mL sealed tubes one by one, heat and stir in an oil bath at 60°C for 8 hours, and track the reaction progress according to TLC. GC-MS determined the exact yield of the product. According to GC and GC-MS, when using DMSO as reaction solvent, inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or trimethylsiliconate potassium (sodium) as catalyst, the yield of product is successively : 67%, 52%, 71%, 59%, 90%, 83%. When using DMA as reaction solvent, inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsiliconate (sodium) are as catalyst, and the yield of product is successively: 51%, 52%, 54%, 55%, 89%, 80%.

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Abstract

The invention relates to an efficient and mild novel method for organosilicone reagent carbon-silicon bond rupture. According to the reaction method, metal alkali which is cheap and easy to obtain is taken as a catalyst, a common commercial solvent serves as a reaction solvent and a hydrogen source, a trimethyl aryl silicon reagent or an aryl alkynyl silicon reagent can be catalyzed smoothly in air under mild conditions to selectively undergo carbon-silicon bond cracking hydrogenation reaction, a substrate is wide in universality, and functional group compatibility is excellent. For the first time the carbon-silicon bond rupture reaction without transition metal catalysis is implemented innovatively, the limitation that in a conventional method, greatly excessively inorganic base or expensive metal catalysts need to be used to perform silicon disprotection is also overcome, and a novel strategy is provided for disprotection of organosilicone groups in lab preparation and industrial production.

Description

technical field [0001] The present invention relates to a novel method for silicon-based deprotection of organosilicon reagents with high efficiency, mildness and non-metal catalysis. Background technique [0002] Since organosilicon reagents were used as protective groups for hydroxyl groups in the 1970s, organosilicon reagents have made very important progress as protective groups in organic reactions, especially trimethylsilyl (TMS) has become the most important in organic synthesis. One of the commonly used protective groups for compounds is widely used in the synthesis of natural products, drug molecules, etc., allowing organic compounds to selectively participate in the reaction, which has attracted widespread attention from scientific researchers. As early as the 1990s, CF 3 COOH (J. Organometallic Chem., 1990, 382, ​​191; J. Chem. Soc. Perkin Trans., 1990, 681), CSF (J. Org. Chem., 1989, 54, 4372; J. Med. Chem., 1991 ,34,1155) and other fluorine-containing ion reag...

Claims

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Application Information

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IPC IPC(8): C07B35/06C07C1/32C07C15/04C07C15/06C07C15/14C07C15/46C07C15/48C07C17/361C07C25/13C07C25/06C07C22/08C07C25/24C07C41/18C07C43/205C07C43/215C07C319/12C07C321/10C07C253/30C07C255/50C07C45/65C07C47/54C07C47/548C07C209/68C07C211/46C07C67/317C07C69/76C07D333/10C07D333/08
CPCC07B35/06C07C1/321C07C15/04C07C15/06C07C15/14C07C15/46C07C15/48C07C17/361C07C22/08C07C25/06C07C25/13C07C25/24C07C41/18C07C43/205C07C43/215C07C45/65C07C47/54C07C47/548C07C67/317C07C69/76C07C209/68C07C211/46C07C253/30C07C255/50C07C319/12C07C321/10C07D333/08C07D333/10Y02P20/52
Inventor 姚武冰
Owner TAIZHOU UNIV
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