A kind of hydroboration method of organic carbonate

Abstract

The invention discloses a method for hydroboration of organic carbonate, which belongs to the technical field of organic compound synthesis. The method is as follows: under the condition of anhydrous and oxygen-free, β-diimine monovalent magnesium compound is added into the mixture of pinacol borane and organic carbonate, and the reaction is stirred at room temperature. In the method for hydroboration of organic carbonates of the present invention, the catalyst β-diimine monovalent magnesium compound has high activity in catalyzing the reaction between organic carbonates and pinacol borane, wide substrate universality, and high reaction catalytic efficiency. The product yield is high and has good practicability.

Description

technical field

[0001] The invention relates to the technical field of hydroboration reaction, in particular to a method for hydroboration of organic carbonates. Background technique

[0002] Organic carbonates are often used as a green solvent and have been widely used in synthesis and catalysis [Schaffner.B, Schaffner.F, Verevkin.S.P, Borner.A, Chem.Rev.2010, 110, 4554-4581] . In recent years, the reduction of organic carbonates has received much attention because these compounds are easily generated from carbon dioxide or carbon monoxide and can be further hydrolyzed to methanol derivatives etc. [Balaraman.E, Gunanathan.C, Zhang.J, Shimon .L.J, Milstein.D, Nat.Chem.2011, 3, 609-614; Han.Z, Rong.L, Wu.J, Zhang.L, Wang.Z, Ding.K, Angew.Chem.Int. Ed .2012, 51, 13041-13045]. On the other hand, cyclic organic carbonates synthesized by the direct coupling reaction of carbon dioxide with ethylene oxide or oxetane can be used as protecting groups or precursors for the synthesi...

Examples

Embodiment 1

[0017] The β-diimine monovalent magnesium compound catalyzes the reaction of ethylene carbonate and pinacol borane, and the process is as follows:

[0018] In the glove box, 1mol% of β-diimine monovalent magnesium compound, 0.4mmol of ethylene carbonate, and 1.6mmol of pinacol borane were successively added to the reaction bottle, and then it was removed from the glove box, stirred for 6h, and tested by nuclear magnetic The spectrum gave a 99% yield.

[0019] Characterize the product, the data are: 1 H NMR (600MHz, CDCl 3 ): 63.86 (s, 4H, OCH 2 ), 1.18(s, 24H, BOCMe 2 ). 13 C{ 1 H} NMR (151MHz, CDCl 3 ): δ82.65 (BOCMe 2 ), 64.98 (OCH 2 ), 24.53 (BOCMe 2 ). 11 B{ 1 H} NMR (193MHz, CDCl 3 ): δ22.24.

[0020] Available, the product structural formula is:

[0021]

Embodiment 2

[0023] The β-diimine monovalent magnesium compound catalyzes the reaction of propylene carbonate and pinacol borane, and the process is as follows:

[0024] In the glove box, 1mol% of β-diimine monovalent magnesium compound, 0.4mmol of propylene carbonate, and 1.6mmol of pinacol borane were successively added to the reaction bottle, and then it was removed from the glove box, stirred for 6h, and analyzed by nuclear magnetic spectrum. The figure gives a yield of 99%.

[0025] Characterize the product, the data are: 1 H NMR (600MHz, CDCl 3 ): δ4.23-4.18 (m, 1H, CH), 3.67 (d, 3 J HH =4.2Hz, 2H, OCH 2 ), 1.17(s, 24H, BOCMe 2 ), 1.09(d, 3 J HH = 6.0 Hz, 3H, Me). 13 C{ 1 H} NMR (151MHz, CDCl 3 ): δ82.70, 82.67 (BOCMe 2 ), 70.32 (OCH 2 ), 69.12(CH), 24.54, 24.53(BOCMe 2 ), 18.46 (Me). 11 B{ 1 H} NMR (193MHz, CDCl 3 ): δ22.19.

[0026] Available, the product structural formula is:

[0027]

Embodiment 3

[0029] The β-diimine monovalent magnesium compound catalyzes the reaction of 4-ethyl-1,3-dioxan-2-one with pinacol borane, and the process is as follows:

[0030] In the glove box, β-diimine monovalent magnesium compound 1mol%, 4-ethyl-1, 3-dioxan-2-one 0.4mmol, pinacol borane 1.6mmol, Then it was removed from the glove box, stirred for 6 h, and the yield was 99% according to nuclear magnetic spectrum.

[0031] Characterize the product, the data are: 1 H NMR (600MHz, CDCl 3 ): δ4.01-3.97 (m, 1H, CH), 3.75-3.65 (m, 2H, OCH2 ), 1.49-1.36 (m, 2H, CH 2 ), 1.17(s, 24H, BOCMe 2 ), 0.84(t, 3 J HH = 7.2Hz, 3H, Me). 13 C{ 1 H} NMR (151MHz, CDCl 3 ): δ82.58, 82.44 (BOCMe 2 ), 75.31(CH), 67.64(OCH 2 ), 25.21 (CH 2 ), 24.51, 24.48 (BOCMe 2 ), 9.40 (Me). 11 B{ 1 H} NMR (193MHz, CDCl 3 ): 622.24.

[0032] Available, the product structural formula is:

[0033]

technical field

[0001] The invention relates to the technical field of hydroboration reaction, in particular to a method for hydroboration of organic carbonates. Background technique

[0002] Organic carbonates are often used as a green solvent and have been widely used in synthesis and catalysis [Schaffner.B, Schaffner.F, Verevkin.S.P, Borner.A, Chem.Rev.2010, 110, 4554-4581] . In recent years, the reduction of organic carbonates has received much attention because these compounds are easily generated from carbon dioxide or carbon monoxide and can be further hydrolyzed to methanol derivatives etc. [Balaraman.E, Gunanathan.C, Zhang.J, Shimon .L.J, Milstein.D, Nat.Chem.2011, 3, 609-614; Han.Z, Rong.L, Wu.J, Zhang.L, Wang.Z, Ding.K, Angew.Chem.Int. Ed .2012, 51, 13041-13045]. On the other hand, cyclic organic carbonates synthesized by the direct coupling reaction of carbon dioxide with ethylene oxide or oxetane can be used as protecting groups or precursors for the synthesi...

Examples

Embodiment 1

[0017] The β-diimine monovalent magnesium compound catalyzes the reaction of ethylene carbonate and pinacol borane, and the process is as follows:

[0018] In the glove box, 1mol% of β-diimine monovalent magnesium compound, 0.4mmol of ethylene carbonate, and 1.6mmol of pinacol borane were successively added to the reaction bottle, and then it was removed from the glove box, stirred for 6h, and tested by nuclear magnetic The spectrum gave a 99% yield.

[0019] Characterize the product, the data are: 1 H NMR (600MHz, CDCl 3 ): 63.86 (s, 4H, OCH 2 ), 1.18(s, 24H, BOCMe 2 ). 13 C{ 1 H} NMR (151MHz, CDCl 3 ): δ82.65 (BOCMe 2 ), 64.98 (OCH 2 ), 24.53 (BOCMe 2 ). 11 B{ 1 H} NMR (193MHz, CDCl 3 ): δ22.24.

[0020] Available, the product structural formula is:

[0021]

Embodiment 2

[0023] The β-diimine monovalent magnesium compound catalyzes the reaction of propylene carbonate and pinacol borane, and the process is as follows:

[0024] In the glove box, 1mol% of β-diimine monovalent magnesium compound, 0.4mmol of propylene carbonate, and 1.6mmol of pinacol borane were successively added to the reaction bottle, and then it was removed from the glove box, stirred for 6h, and analyzed by nuclear magnetic spectrum. The figure gives a yield of 99%.

[0025] Characterize the product, the data are: 1 H NMR (600MHz, CDCl 3 ): δ4.23-4.18 (m, 1H, CH), 3.67 (d, 3 J HH =4.2Hz, 2H, OCH 2 ), 1.17(s, 24H, BOCMe 2 ), 1.09(d, 3 J HH = 6.0 Hz, 3H, Me). 13 C{ 1 H} NMR (151MHz, CDCl 3 ): δ82.70, 82.67 (BOCMe 2 ), 70.32 (OCH 2 ), 69.12(CH), 24.54, 24.53(BOCMe 2 ), 18.46 (Me). 11 B{ 1 H} NMR (193MHz, CDCl 3 ): δ22.19.

[0026] Available, the product structural formula is:

[0027]

Embodiment 3

[0029] The β-diimine monovalent magnesium compound catalyzes the reaction of 4-ethyl-1,3-dioxan-2-one with pinacol borane, and the process is as follows:

[0030] In the glove box, β-diimine monovalent magnesium compound 1mol%, 4-ethyl-1, 3-dioxan-2-one 0.4mmol, pinacol borane 1.6mmol, Then it was removed from the glove box, stirred for 6 h, and the yield was 99% according to nuclear magnetic spectrum.

[0031] Characterize the product, the data are: 1 H NMR (600MHz, CDCl 3 ): δ4.01-3.97 (m, 1H, CH), 3.75-3.65 (m, 2H, OCH2 ), 1.49-1.36 (m, 2H, CH 2 ), 1.17(s, 24H, BOCMe 2 ), 0.84(t, 3 J HH = 7.2Hz, 3H, Me). 13 C{ 1 H} NMR (151MHz, CDCl 3 ): δ82.58, 82.44 (BOCMe 2 ), 75.31(CH), 67.64(OCH 2 ), 25.21 (CH 2 ), 24.51, 24.48 (BOCMe 2 ), 9.40 (Me). 11 B{ 1 H} NMR (193MHz, CDCl 3 ): 622.24.

[0032] Available, the product structural formula is:

[0033]

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