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Boron esterification reaction method of alkyl bromide without transition metal catalysis

A technology of alkyl bromide and alkyl boronate, applied in the field of boron esterification reaction without transition metal catalysis, can solve the problems of artificial synthesis, high cost, sensitivity, etc. rate effect

Active Publication Date: 2020-03-17
PEKING UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although these methods have been widely used, they still have obvious deficiencies in the following aspects: (1) the metal-ligand combination needs to be complex and rigorously screened, which is time-consuming and laborious; (2) due to the use of transition metal catalysts and strong bases, The reaction is usually very sensitive to air and moisture, and the cost is high; (3) stoichiometric Grignard reagent or organolithium reagent is required for Fe / Mn catalysis, and it is not easy to handle after the reaction
(4) Reaction raw materials are limited, most of them are alkyl iodides with higher activity, which need to be synthesized artificially, and the cost is high

Method used

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  • Boron esterification reaction method of alkyl bromide without transition metal catalysis
  • Boron esterification reaction method of alkyl bromide without transition metal catalysis
  • Boron esterification reaction method of alkyl bromide without transition metal catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035]In a glove box under a nitrogen atmosphere, sequentially add B to a 10 mL Schlenk bottle equipped with a stir bar 2 cat 2 (0.45mmol, 1.5eq, 107.0mg), AIBN (0.33mmol, 1.1eq, 54.2mg), 2mL solvent N,N-dimethylacetamide, TTMSS (0.33mmol, 1.1eq, 101.8μL) and Octane (0.3 mmol, 52.3 μL). The capped Schlenk bottle was removed from the glove box, and the reaction mixture was stirred at 80 °C for 6 hours. After cooling to room temperature, pinacol (141.8 mg, 4.0 equivalents) was added to the reaction flask, 1.0 mL of triethylamine was added, and stirred at room temperature for 1 hour. Subsequently, the reaction mixture was transferred to a 125mL separatory funnel by 30mL ethyl acetate, then 30mL water was added thereto for washing, and then the aqueous phase was extracted 3 times with 30mL ethyl acetate, and the organic phases were combined and transferred to a 250mL separatory funnel, Washed with 100 mL of saturated brine, the organic phase was dried with anhydrous sodium sulf...

Embodiment 2

[0037] In a glove box under a nitrogen atmosphere, sequentially add B to a 10 mL Schlenk bottle equipped with a stir bar 2 cat 2 (0.75mmol, 1.5eq, 178.4mg), AIBN (0.55mmol, 1.1eq, 90.3mg), 3mL solvent N,N-dimethylacetamide, TTMSS (0.55mmol, 1.1eq, 169.7μL) and 6-bromo Methyl hexanoate (0.5 mmol, 79.4 μL). The capped Schlenk bottle was removed from the glove box, and the reaction mixture was stirred at 80 °C for 6 hours. After cooling to room temperature, pinacol (236.3 mg, 4.0 equivalents) was added to the reaction flask, 1.5 mL of triethylamine was added, and stirred at room temperature for 1 hour. Subsequently, the reaction mixture was transferred to a 125mL separatory funnel by 30mL ethyl acetate, then 30mL water was added thereto for washing, and then the aqueous phase was extracted 3 times with 30mL ethyl acetate, and the organic phases were combined and transferred to a 250mL separatory funnel, Washed with 100 mL of saturated brine, the organic phase was dried over an...

Embodiment 3

[0039] In a glove box under a nitrogen atmosphere, sequentially add B to a 10 mL Schlenk bottle equipped with a stir bar 2 cat 2 (0.75mmol, 1.5eq, 178.4mg), AIBN (0.55mmol, 1.1eq, 90.3mg), 3mL solvent N,N-dimethylacetamide, TTMSS (0.55mmol, 1.1eq, 169.7μL) and bromocyclic Heptane (0.5 mmol, 68.7 μL). The capped Schlenk bottle was removed from the glove box, and the reaction mixture was stirred at 80 °C for 6 hours. After cooling to room temperature, pinacol (236.3 mg, 4.0 equivalents) was added to the reaction flask, 1.5 mL of triethylamine was added, and stirred at room temperature for 1 hour. Subsequently, the reaction mixture was transferred to a 125mL separatory funnel by 30mL ethyl acetate, then 30mL water was added thereto for washing, and then the aqueous phase was extracted 3 times with 30mL ethyl acetate, and the organic phases were combined and transferred to a 250mL separatory funnel, Washed with 100 mL of saturated brine, the organic phase was dried with anhydro...

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Abstract

The invention discloses a boron esterification reaction method of alkyl bromide without transition metal catalysis. The method includes: in the absence of a metal catalyst, dissolving 1 equivalent ofalkyl bromide, 1-5 equivalent of diborate, 1-5 equivalent of silane and 1-5 equivalent of a free radical initiator in an organic solvent, sealing the reaction system, and carrying out stirring reaction at 20-150DEG C to obtain alkyl borate. The method for synthesis of alkyl borate from alkyl bromide is simple and efficient, has no need for transition metal catalysis, and only needs diborate serving as a boron source, silane and the free radical initiator are added for reaction under a heating condition, the method shows wide functional group compatibility, can convert various alkyl bromides into borate thereof, and has considerable yield. The obtained product alkyl borate can be applied to Suzuki coupling and other important reactions in the organic synthesis field, and then can be converted into a series of compounds with application value.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a boron esterification method of an alkyl bromide without transition metal catalysis, which can effectively convert a carbon-bromine bond into a carbon-boron bond. Background technique [0002] Organoboron compounds are important intermediates in organic synthesis. They can convert carbon-boron bonds into carbon-carbon and other chemical bonds by methods such as Suzuki coupling, which is of great significance in the field of organic synthesis. For alkyl borates, the traditional method is to use highly active reagents such as Grignard reagents or organolithium reagents as raw materials, but these methods have obvious limitations in terms of functional group compatibility and regioselectivity. In this context, transition metal-catalyzed borylation of alkyl halides has become a general method for the synthesis of alkyl borates, including Cu, Ni, Pd, Fe, Mn, and Zn. It has the abili...

Claims

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Application Information

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IPC IPC(8): C07F5/02
CPCC07F5/025
Inventor 孙北奇赵玉孙洋王宏刚莫凡洋
Owner PEKING UNIV
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