Method for preparing borate ester on basis of tricyclopentadienyl rare earth metal complex

Abstract

Disclosed is a method for preparing a borate ester on the basis of a tricyclopentadienyl rare earth metal complex, the method comprising the following steps: uniformly stirring and mixing a catalyst, a borane and a carbonyl compound for reaction to prepare a borate ester, wherein the catalyst is a tricyclopentadienyl rare earth metal complex; and the molecular formula of the tricyclopentadienyl rare earth metal complex can be expressed as: Ln(Cp).sub.3, wherein Ln represents a rare metal selected from one of lanthanide elements. The preparation method has a higher catalytic activity, mild reaction conditions, a product that is easy to post-treat, a short reaction time, a low catalyst consumption amount, and a good range of applicable substrates, and can be used for industrial production.

Claims

1. A method for preparing a borate ester in the presence of a tricyclopentadienyl rare earth metal complex, the method comprising the following steps: uniformly stirring and mixing a catalyst, a borane and a carbonyl compound in a reaction to prepare the borate ester, wherein the catalyst is a tricyclopentadienyl rare earth metal complex; wherein the carbonyl compound is a ketone or an aldehyde; wherein the chemical formula of the tricyclopentadienyl rare earth metal complex is expressed as: ##STR00011## wherein Ln represents a rare earth metal.

2. The method according to claim 1, wherein the borane is pinacolborane; wherein the ketone is an aromatic ketone or an aliphatic cyclic ketone; wherein the chemical formula of the aromatic ketone is represented by one of the following: ##STR00012## wherein R1 is phenyl, substituted-phenyl or heterocyclic aryl group; wherein the chemical formula of the aliphatic cyclic ketone is represented by one of the following: ##STR00013## wherein n is 3-15; wherein the chemical structural formula of aldehyde is represented by one of the following: ##STR00014## wherein R is hydrogen, halogen, methyl or methoxy group.

3. The method according to claim 1, wherein an amount of the tricyclopentadienyl rare earth metal complex is 0.01-1% of a molar amount of carbonyl compound; wherein a molar ratio of the borane and the carbonyl compound is 1-1.2:1.

4. The method according to claim 1, wherein the reaction is carried out in an organic solvent; wherein a reaction time is between 30 min and 1 h; wherein the reaction is carried out at room temperature.

5. The method according to claim 1, further comprising: when the reaction is over, reducing pressure and removing solvent of reaction solution, adding n-hexane into a residual liquid, and obtaining various substituted borate esters.

6. A method comprising applying a tricyclopentadienyl rare earth metal complex as a catalyst for a reaction of a carbonyl compound with pinacolborane; wherein the chemical formula of the tricyclopentadienyl rare earth metal complex is: ##STR00015## wherein Ln represents a rare earth metal.

7. The method according to claim 6, wherein Ln is a rare-earth metal selected from the group consisting of lanthanum, yttrium, neodymium, ytterbium and samarium; wherein the borane is pinacolborane; wherein the carbonyl compound is a ketone or an aldehyde; wherein the ketone is an aromatic ketone or an aliphatic cyclic ketone; wherein the chemical formula of the aromatic ketone is represented by: ##STR00016## wherein R1 is phenyl, substituted-phenyl or heterocyclic aryl group; wherein the chemical formula of the aliphatic cyclic ketone is represented by one of the following: ##STR00017## wherein n is 3-15; wherein the chemical formula of the aldehyde is represented by one of the following: ##STR00018## wherein R is hydrogen, halogen, methyl or methoxy group.

8. The method according to claim 6, wherein of the tricyclopentadienyl rare earth metal complex is 0.01-1% of a molar amount of the carbonyl compound; wherein a molar ratio of the pinacolborane and the carbonyl compound is 1-1.2:1; wherein a reaction time is between 30 min and 1 h; wherein the reaction is carried out at room temperature.

9. A method for reaction of a borane with an aldehyde, the method comprising the following steps: uniformly stirring and mixing the borane and the aldehyde in the presence of a catalyst, completely reacting the borane with the aldehyde at room temperature for 30 min to 1 h; wherein the catalyst is a tricyclopentadienyl rare earth metal complex having a chemical formula represented by: ##STR00019## wherein Ln represents a rare earth metal.

Description

EMBODIMENT OF INVENTION

Embodiment of the Present Invention

Example 1: Benzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by Y(Cp).SUB.3

(1) At the inert gas, loading the tetrahydrofuran solution of Y(Cp).sub.3 catalyst (1 mol %) to the reaction bottle which is treated by dehydration and deoxidation, then adding a pinacolborane (145.1 μL, 1 mmol) with pipette gun, and then adding a benzaldehyde (101.1 μL, 1 mmol) with pipette gun, after reacting for 30 minutes at room temperature, the stock solution is added CDCl.sub.3. After calculation, conversion rate of 1H is 98%. .sup.1H NMR analysis of the product is: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.37-7.31 (m, 4 h), 7.27 (DT, j=6.1, 3.3 hz, 1H), 4.94 (s, 2 h), 1.27 (s, 12 h).

Example 2: Benzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by Y(Cp).SUB.3

(2) At the inert gas, loading the tetrahydrofuran solution of Y(Cp).sub.3 catalyst (0.2 mol %) to the reaction bottle which is treated by dehydration and deoxidation, then adding a pinacolborane (145.1 μL, 1 mmol) with pipette gun, and then adding a benzaldehyde (101.1 μL, 1 mmol) with pipette gun, after reacting for 30 minutes at room temperature, the stock solution is added CDCl.sub.3. After calculation, conversion rate of .sup.1H is 97%. .sup.1H NMR analysis of the product is the same with Examples 1.

Example 3: Benzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by Y(Cp).SUB.3

(3) At the inert gas, loading the tetrahydrofuran solution of Y(Cp).sub.3 catalyst (0.1 mol %) to the reaction bottle which is treated by dehydration and deoxidation, then adding a pinacolborane (145.1 μL, 1 mmol) with pipette gun, and then adding a benzaldehyde (101.1 μL, 1 mmol) with pipette gun, after reacting for 30 minutes at room temperature, the stock solution is added CDCl.sub.3. After calculation, conversion rate of .sup.1H is 96%. .sup.1H NMR analysis of the product is the same with Examples 1.

Example 4: Benzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by Y(Cp).SUB.3

(4) At the inert gas, loading the tetrahydrofuran solution of Y(Cp).sub.3 catalyst (1 mol %) to the reaction bottle which is treated by dehydration and deoxidation, then adding a pinacolborane (145.1 μL, 1 mmol) with pipette gun, and then adding a benzaldehyde (101.1 μL, 1 mmol) with pipette gun, after reacting for 60 minutes at room temperature, the stock solution is added CDCl.sub.3. After calculation, conversion rate of .sup.1H is 99%. .sup.1H NMR analysis of the product is the same with Examples 1.

(5) Replace Y with Nd, Sm, Yb, conversion rate of .sup.1H more than 99%, 99%, 99%.

Example 5: Benzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(6) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.7 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (2 ml), then adding mixture (22 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding benzaldehyde (101.6 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 100%. .sup.1H NMR analysis of the product is the same with Examples 1.

Example 6: Benzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(7) At the inert gas, loading the La(Cp).sub.3 catalyst (3.7 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (2 ml), then adding mixture (22 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding benzaldehyde (101.6 μL, 1 mmol) with pipette gun, after reacting for 30 min at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is more than 99%. .sup.1H NMR analysis of the product is the same with Examples 1.

Example 7: Benzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(8) At the inert gas, Loading the La(Cp).sub.3 catalyst (5 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (24.4 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (145.1 μL, 1 mmol) with pipette gun, and then adding benzaldehyde (101.6 μL, 1 mmol) with pipette gun, after reacting for 30 min at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is more than 99%. .sup.1H NMR analysis of the product is the same with Examples 1.

Example 8: 4-Methylbenzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(9) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.7 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (2 ml), then adding mixture (22 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 4-methylbenzaldehyde (117.9 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 100%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.37-7.31 (m, 4H), 7.27 (dt, J=6.1, 3.3 Hz, 1H), 4.94 (s, 2H), 1.27 (s, 12H).

Example 9: 2-Methylbenzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(10) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.7 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (2 ml), then adding mixture (22 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 2-methylbenzaldehyde (115.6 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 100%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.37-7.31 (m, 4H), 7.27 (dt, J=6.1, 3.3 Hz, 1H), 4.94 (s, 2H), 1.27 (s, 12H).

Example 10: 2,4,6-Trimethylbenzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(11) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.7 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (2 ml), then adding mixture (22 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 2,4,6-trimethylbenzaldehyde (147.5 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 100%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.37-7.31 (m, 4H), 7.27 (dt, J=6.1, 3.3 Hz, 1H), 4.94 (s, 2H), 1.27 (s, 12H).

Example 11: 2-Methoxybenzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(12) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.7 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (2 ml), then adding mixture (22 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 2-methoxybenzaldehyde (120.8 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 100%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.41 (dd, J=7.5, 0.7 Hz, 1H), 7.23 (dd, J=7.8, 1.4 Hz, 1H), 6.95 (t, J=7.5 Hz, 1H), 6.84 (d, J=8.1 Hz, 1H), 4.98 (s, 2H), 3.81 (s, 3H), 1.34-1.21 (m, 12H).

Example 12: 4-Chlorobenzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(13) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.5 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (24.4 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 4-chlorobenzaldehyde (117.5 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 100%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.36 (s, 1H), 7.26-7.18 (m, 3H), 4.89 (s, 2H), 1.27 (s, 12H).

Example 13: 4-Bromobenzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(14) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.5 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (18.5 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (132 μL, 0.91 mmol) with pipette gun, and then adding 4-bromobenzaldehyde (140.3 μL, 0.76 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 99%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.36 (s, 1H), 7.26-7.18 (m, 3H), 4.89 (s, 2H), 1.27 (s, 12H).

Example 14: 2-Chlorobenzaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(15) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.5 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (18.5 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 2-chlorobenzaldehyde (117.5 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 100%.

Example 15: Isovaleraldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(16) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.5 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (18.5 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding isovaleraldehyde (1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is more than 99%.

Example 16: 3-Pyridylaldehyde with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(17) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.5 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (18.5 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 3-pyridylaldehyde (1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is more than 99%.

Example 17: Hypnone with Pinacolborane Compound into the Borate Ester Catalyzed by Y(Cp).SUB.3

(18) At the inert gas, Loading the Y(Cp).sub.3 catalyst (5.2 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (20.6 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding hypnone (116.7 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 98%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.40-7.22 (m, 5H), 1.51-1.47 (d, J=6.5 Hz, 3H), 1.24 (s, 6H), 1.21 (s, 6H).

Example 18: Hypnone with Pinacolborane Compound into the Borate Ester Catalyzed by Nd(Cp).SUB.3

(19) At the inert gas, Loading the Nd(Cp).sub.3 catalyst (5.3 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (23.3 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding hypnone (116.7 μL, 1 mmol) with pipette gun, after reacting for 60 minutes at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is more than 99%. .sup.1H NMR analysis of the product is the same with Examples 17.

Example 19: Hypnone with Pinacolborane Compound into the Borate Ester Catalyzed by Sm(Cp).SUB.3

(20) At the inert gas, Loading the Sm(Cp).sub.3 catalyst (2.1 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (2 ml), then adding mixture (39.8 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding hypnone (116.7 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 99%. .sup.1H NMR analysis of the product is the same with Examples 17.

Example 20: Hypnone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(21) At the inert gas, Loading the La(Cp).sub.3 catalyst (2.8 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (2 ml), then adding mixture (29 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding hypnone (116.7 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is more than 99%. .sup.1H NMR analysis of the product is the same with Examples 17.

(22) ##STR00010##

Example 21: Hypnone with Pinacolborane Compound into the Borate Ester Catalyzed by Yb(Cp).SUB.3

(23) At the inert gas, Loading the Yb(Cp).sub.3 catalyst (4.3 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (30.7 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding hypnone (116.7 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 97%. .sup.1H NMR analysis of the product is the same with Examples 17.

Example 22: Isobutyrophenone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(24) At the inert gas, Loading the La(Cp).sub.3 catalyst (4.8 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (4 ml), then adding mixture (33.8 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding isobutyrophenone (150 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 99%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.34-7.26 (m, 4H), 7.25-7.19 (m, 1H), 4.81 (d, J=6.2 Hz, 1H), 1.96 (dq, J=13.4, 6.7 Hz, 1H), 1.21 (s, 6H), 1.17 (s, 6H), 0.90 (d, J=6.7 Hz, 3H), 0.83 (d, J=6.8 Hz, 3H).

Example 23: 4-Methoxyacetophenone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(25) At the inert gas, Loading the La(Cp).sub.3 catalyst (4.8 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (4 ml), then adding mixture (37.1 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (190.8 μL, 1.3 mmol) with pipette gun, and then adding 4-methoxyacetophenone (164.6 mg, 1.1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 100%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.38-7.17 (m, 2H), 6.94-6.68 (m, 2H), 5.20 (q, J=6.4 Hz, 1H), 3.79 (s, 3H), 1.47 (d, J=6.4 Hz, 3H), 1.24 (s, 6H), 1.22 (s, 6H).

Example 24: 4-Fluoroacetophenone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(26) At the inert gas, Loading the La(Cp).sub.3 catalyst (7 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (5 ml), then adding mixture (29 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 4-fluoroacetophenone (120.9 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 99%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.38-7.29 (m, 2H), 7.05-6.94 (m, 2H), 5.21 (q, J=6.4 Hz, 1H), 1.47 (d, J=6.4 Hz, 3H), 1.24 (s, 6H), 1.21 (s, 6H).

Example 25: 4-Methylacetophenone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(27) At the inert gas, Loading the La(Cp).sub.3 catalyst (7 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (5 ml), then adding mixture (29 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 4-methylacetophenone (133.5 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is more than 99%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.31-7.25 (m, 2H), 7.16 (t, J=7.4 Hz, 2H), 5.24 (q, J=6.4 Hz, 1H), 2.35 (s, 3H), 1.27 (s, 6H), 1.24 (s, 6H).

Example 26: 1-Tetralone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(28) At the inert gas, Loading the La(Cp).sub.3 catalyst (7 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (5 ml), then adding mixture (29 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 1-tetralone (132.8 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is more than 99%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.43-7.35 (m, 1H), 7.19-7.13 (m, 2H), 7.08 (m, 4.9 Hz, 1H), 2.94-2.58 (m, 2H), 2.14-1.99 (m, 1H), 2.00-1.90 (m, 2H), 1.82-1.67 (m, 1H), 1.31 (s, 6H), 1.29 (s, 6H).

Example 27: 2-Methylacetophenone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(29) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.9 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (9 ml), then adding mixture (31.3 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 2-methylacetophenone (130.8 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 99%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.55 (m, 1H), 7.33-7.08 (m, 3H), 5.45 (q, J=6.4 Hz, 1H), 1.48 (d, J=6.4 Hz, 3H), 1.26 (s, 6H), 1.22 (s, 6H).

Example 28: 2,4,6-Trimethylacetophenone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(30) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.9 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (31.3 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174 μL, 1.2 mmol) with pipette gun, and then adding 2,4,6-trimethylacetophenone (166.4 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 99%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 6.79 (s, 2H), 5.65 (q, J=6.8 Hz, 1H), 2.41 (s, 6H), 2.24 (s, 3H), 1.52 (d, J=6.8 Hz, 3H), 1.21 (s, 6H), 1.17 (s, 6H).

Example 29: 4-Bromoacetophenone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(31) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.9 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (38 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (211.5 μL, 1.4 mmol) with pipette gun, and then adding 4-bromoacetophenone (241.8 mg, 1.2 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 98%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.41 (m, 2H), 7.21 (m, 2H), 5.16 (q, J=6.4 Hz, 1H), 1.42 (d, J=6.5 Hz, 3H), 1.20 (s, 6H), 1.18 (s, 6H).

Example 30: 4-Nitroacetophenone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(32) At the inert gas, Loading the La(Cp).sub.3 catalyst (3.9 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (3 ml), then adding mixture (31.8 μL, 0.01 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (177 μL, 1.2 mmol) with pipette gun, and then adding 4-nitroacetophenone (167.9 mg, 1 mmol) with pipette gun, after reacting for 2 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 98%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.16-8.08 (m, 2H), 7.47 (m, 2H), 5.26 (q, J=6.5 Hz, 1H), 1.44 (d, J=6.5 Hz, 3H), 1.19 (s, 6H), 1.16 (s, 6H).

Example 31: 1-(2-Thienyl) Acetone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(33) At the inert gas, Loading the La(Cp).sub.3 catalyst (18.5 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (1.6 ml), then adding mixture (353 μL, 1 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (174.1 μL, 1.2 mmol) with pipette gun, and then adding 1-(2-thienyl) acetone (108 μL, 1 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 99%. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.21-7.19 (m, 1H), 6.97-6.92 (m, 2H), 5.48 (q, J=6.4 Hz, 1H), 1.60 (d, J=6.4 Hz, 3H), 1.25 (d, J=4.9 Hz, 12H).

Example 32: Cyclododecanone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(34) At the inert gas, Loading the La(Cp).sub.3 catalyst (18.5 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (1.6 ml), then adding mixture (340.8 μL, 1 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (168.8 μL, 1.16 mmol) with pipette gun, and then adding cyclododecanone (168.8 mg, 0.97 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 100%, and conversion rate of .sup.1H is 99% under 0.01 mol % with catalyst. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 4.11 (dt, J=31.5, 15.5 Hz, 1H), 1.66-1.53 (m, 2H), 1.32 (m, 22H), 1.17 (s, 12H).

Example 33: 1,3-Diphenylacetone with Pinacolborane Compound into the Borate Ester Catalyzed by La(Cp).SUB.3

(35) At the inert gas, Loading the La(Cp).sub.3 catalyst (18.5 mg) to the reaction bottle which is treated by dehydration and deoxidation, then adding tetrahydrofuran (1.6 ml), then adding mixture (286 μL, 1 mol %) with pipette gun to another reaction bottle, then adding pinacolborane (142.2 μL, 0.98 mmol) with pipette gun, and then adding 1,3-diphenylacetone (171.7 mg, 0.82 mmol) with pipette gun, after reacting for 1 h at room temperature, then pipette a drop into the nucleus tube and added CDCl.sub.3 formulated solution. After calculation, conversion rate of .sup.1H is 100%, and conversion rate of .sup.1H is 99% under 0.01 mol % with catalyst. .sup.1H NMR analysis of the product: .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.26-7.12 (m, 10H), 4.42 (dt, J=8.7, 4.5 Hz, 1H), 2.78 (m, 4H), 0.90 (s, 12H).