Method for preparation of gem-diboron compound by olefin selective 1, 1-diboronation

Abstract

The invention relates to a method for preparation of a gem-diboron compound by olefin selective 1, 1-diboronation. The method includes: dissolving an olefin compound, a cyclopentadienyl early transition metal catalyst and an alkali compound in a solvent, then adding a borane compound, carrying out reaction at 60-150DEG C for 1-16h in a protective atmosphere, and then carrying out separation to obtain the gem-diboron compound. The method is simple and convenient to operate, low in cost, and high in reaction atom economy, and is suitable for industrial production.

Description

technical field

[0001] The invention relates to the technical field of organic synthesis and transition metal catalysis, in particular to a method for preparing gem-diboron compounds by selective 1,1-diboration of alkenes. Background technique

[0002] As an important intermediate in synthetic chemistry, organoboron compounds are widely used in research fields such as material science and pharmaceutical industry. In recent years, more and more chemists have paid more and more attention to the synthesis and application of polyboron compounds, in which gem-diboron compounds refer to organoboron compounds with two boron units connected on the same carbon. Because it contains two boron units, it means that it has more reaction sites, which also provides more transformation pathways and methods for the construction of complex molecules, and is a very useful synthetic intermediate and pharmaceutical precursor compound.

[0003] In view of the potential application value of gem-d...

Examples

Embodiment 1

[0022] Example 1 A method for the selective 1,1-diboration of olefins to prepare gem-diboron compounds:

[0023]

[0024] Add Cp to the reaction tube sequentially 2 ZrCl 2 (0.01 mmol, 2.9 mg), MeOLi (0.2 mmol, 7.6 mg), toluene (1 mL), pinacol borane 2a (0.6 mmol, 87 μL), styrene 1a (0.2 mmol, 23 μL), in nitrogen (1 atm) atmosphere at 100 °C for 8 h. GC-MS detection yield was 88%.

Embodiment 2

[0025] Example 2 A method for the selective 1,1-diboration of olefins to prepare gem-diboron compounds:

[0026]

[0027] Add Cp to the reaction tube sequentially 2 ZrCl 2 (0.01 mmol, 2.9 mg), MeOLi (0.2 mmol, 7.6 mg), toluene (1 mL), pinacol borane 2a (0.6 mmol, 87 μL), styrene 1a (0.2 mmol, 23 μL), in nitrogen (1 atm) atmosphere at 130 °C for 2 h. GC-MS detection yield was 92%.

Embodiment 3

[0028] Example 3 A method for the selective 1,1-diboration of olefins to prepare gem-diboron compounds:

[0029]

[0030] Add Cp to the reaction tube sequentially 2 ZrCl 2 (0.01 mmol, 2.9 mg), MeOLi (0.2 mmol, 7.6 mg), toluene (1 mL), pinacol borane 2a (0.6 mmol, 87 μL), styrene 1a (0.2 mmol, 23 μL), in nitrogen (1 atm) atmosphere at 80 °C for 16 h. GC-MS detection yield was 81%.

technical field

[0001] The invention relates to the technical field of organic synthesis and transition metal catalysis, in particular to a method for preparing gem-diboron compounds by selective 1,1-diboration of alkenes. Background technique

[0002] As an important intermediate in synthetic chemistry, organoboron compounds are widely used in research fields such as material science and pharmaceutical industry. In recent years, more and more chemists have paid more and more attention to the synthesis and application of polyboron compounds, in which gem-diboron compounds refer to organoboron compounds with two boron units connected on the same carbon. Because it contains two boron units, it means that it has more reaction sites, which also provides more transformation pathways and methods for the construction of complex molecules, and is a very useful synthetic intermediate and pharmaceutical precursor compound.

[0003] In view of the potential application value of gem-d...

Examples

Embodiment 1

[0022] Example 1 A method for the selective 1,1-diboration of olefins to prepare gem-diboron compounds:

[0023]

[0024] Add Cp to the reaction tube sequentially 2 ZrCl 2 (0.01 mmol, 2.9 mg), MeOLi (0.2 mmol, 7.6 mg), toluene (1 mL), pinacol borane 2a (0.6 mmol, 87 μL), styrene 1a (0.2 mmol, 23 μL), in nitrogen (1 atm) atmosphere at 100 °C for 8 h. GC-MS detection yield was 88%.

Embodiment 2

[0025] Example 2 A method for the selective 1,1-diboration of olefins to prepare gem-diboron compounds:

[0026]

[0027] Add Cp to the reaction tube sequentially 2 ZrCl 2 (0.01 mmol, 2.9 mg), MeOLi (0.2 mmol, 7.6 mg), toluene (1 mL), pinacol borane 2a (0.6 mmol, 87 μL), styrene 1a (0.2 mmol, 23 μL), in nitrogen (1 atm) atmosphere at 130 °C for 2 h. GC-MS detection yield was 92%.

Embodiment 3

[0028] Example 3 A method for the selective 1,1-diboration of olefins to prepare gem-diboron compounds:

[0029]

[0030] Add Cp to the reaction tube sequentially 2 ZrCl 2 (0.01 mmol, 2.9 mg), MeOLi (0.2 mmol, 7.6 mg), toluene (1 mL), pinacol borane 2a (0.6 mmol, 87 μL), styrene 1a (0.2 mmol, 23 μL), in nitrogen (1 atm) atmosphere at 80 °C for 16 h. GC-MS detection yield was 81%.

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