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Method for synthesizing alpha-borocarbonyl compound through B-H bond insertion reaction with iridium as catalyst and sulfur ylide as Carbene precursor

A carbonyl compound and insertion reaction technology, applied in the field of molecular entities - α-boronocarbonyl compounds, can solve the problems of cumbersome steps, harsh conditions, low yields, etc., and achieve broad application prospects and good substrate applicability.

Inactive Publication Date: 2019-12-20
SICHUAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Solve the problems of cumbersome steps, harsh conditions, unstable raw materials, low yields, expensive catalysts, and low atom utilization in the various methods reported before

Method used

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  • Method for synthesizing alpha-borocarbonyl compound through B-H bond insertion reaction with iridium as catalyst and sulfur ylide as Carbene precursor
  • Method for synthesizing alpha-borocarbonyl compound through B-H bond insertion reaction with iridium as catalyst and sulfur ylide as Carbene precursor
  • Method for synthesizing alpha-borocarbonyl compound through B-H bond insertion reaction with iridium as catalyst and sulfur ylide as Carbene precursor

Examples

Experimental program
Comparison scheme
Effect test

Embodiment example 1

[0011] Implementation Case 1: Synthesis of Compound 1

[0012]

[0013] Add sulfur ylide (0.15 mmol), borane adduct (0.6 mmol), [Ir(COD)Cl] 2 (5 mol %) and CuF 2 (20 mol%). Then add 10ml of PhCl, stir at 60°C for 3h, and TLC detects that the reaction is complete. Then it was diluted with EA, and the solvent was removed under reduced pressure. It was separated and purified by PE / EA silica gel chromatography to obtain a white solid with a melting point of 59-61° C. and a yield of 94%.

[0014] 1 (400 MHz, Chloroform- d ) δ 8.00 (d, J = 7.2 Hz, 2H), 7.47 (t, J =7.2 Hz, 1H), 7.40 (t, J = 7.2 Hz, 2H), 2.61 (s, 9H), 2.46 (t, J = 5.2 Hz,2H); 13 C NMR (101 MHz, Chloroform- d ) δ 208.09, 138.12, 131.84, 128.79, 128.13, 52.29, 29.84; 11 B NMR (128 MHz, Chloroform- d ) δ -3.74 (t, J B-H = 101.9 Hz); HRMS (ESI) m / z Calculated value [C 11 h 18 BNNaO, M + Na] + : 214.0708; Found: 214.0710.

Embodiment example 2

[0015] Implementation Case 2: Synthesis of Compound 2

[0016]

[0017] Add sulfur ylide (0.15 mmol), borane adduct (0.6 mmol), [Ir(COD)Cl] 2 (5 mol %) and CuF 2 (20 mol%). Then add 10ml of PhCl, stir at 60°C for 3h, and TLC detects that the reaction is complete. Then it was diluted with EA, and the solvent was removed under reduced pressure. It was separated and purified by PE / EA silica gel chromatography to obtain a white solid with a melting point of 64-65°C and a yield of 81%.

[0018] 1 H NMR (400 MHz, Chloroform- d ) δ 7.50 (dd, J = 1.6, 0.8 Hz, 1H), 7.09(dd, J = 3.6, 0.8 Hz, 1H), 6.45 (dd, J = 3.6, 1.6 Hz, 1H), 2.61 (s, 9H), 2.30(t, J = 5.2 Hz, 2H); 13 C NMR (101 MHz, Chloroform- d ) δ 197.15, 153.66, 145.15, 116.16, 111.67, 52.34, 29.84; 11 B NMR (128 MHz, Chloroform- d ) δ -3.10 (t, J B-H = 103.0 Hz); HRMS (ESI) m / z Calculated value [C 9 h 16 BYZGR 2 , M + Na] + : 204.1172; Found: 224.1175.

Embodiment example 3

[0019] Implementation Case 3: Synthesis of Compound 3

[0020]

[0021] Add sulfur ylide (0.15 mmol), borane adduct (0.6 mmol), [Ir(COD)Cl] 2 (20 mol %) and CuF 2 (2.0 eq). Then add 10ml of PhCl, stir at 60°C for 3h, and TLC detects that the reaction is complete. Then it was diluted with EA, and the solvent was removed under reduced pressure. It was separated and purified by PE / EA silica gel chromatography to obtain a white solid with a melting point of 45-47° C. and a yield of 97%.

[0022] 1 (400 MHz, Chloroform- d ) δ 2.57 (s, 9H), 1.96 (d, J = 5.2 Hz, 2H),1.83 – 1.60 (m, 8H), 1.34 – 1.26 (m, 3H), 1.24 – 1.17 (m, 2H). 13 C NMR (101MHz, Chloroform- d ) δ 222.18, 52.33, 49.85, 29.84, 29.34, 26.24, 26.16; 11 B NMR (128 MHz, Chloroform- d ) δ -4.52 (t, J B-H = 101.3 Hz); HRMS (ESI) m / z Calculated value [C 11 h 24 BNNaO, M + Na] + :220.1849; Found: 220.1845.

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Abstract

The invention relates to a method for efficiently synthesizing an alpha-borocarbonyl compound through B-H insertion reaction with iridium as a catalyst and sulfur ylide as a Carbene precursor and lewis base borane adduct. Compared with other methods, the method has the advantages that the raw materials are stable and easy to obtain, the steps are simple, the conditions are mild, the method can effectively prepare the important molecular entity, namely the alpha-borocarbonyl compound, in organic synthesis, and the method has wide application prospects.

Description

technical field [0001] The invention relates to a kind of Ir-catalyzed, sulfur ylide as carbene precursor and Lewis base borane adduct B-H intercalation reaction mild and efficient synthesis of important molecular entity in organic synthesis - α-boronocarbonyl compound, which belongs to chemistry synthetic field. Background technique [0002] Organoboron compounds are widely used in medicine, materials chemistry, organic synthesis, etc., and several effective methods have been reported to build C-B bonds 1-4 . Among them, α-borocarbonyl compounds have recently been recognized as important molecular entities in organic synthesis due to their amphoteric properties. 5 . However, so far, there are few reports on the synthesis of stable and separable α-boronocarbonyl compounds, and the related methods have the disadvantages of low yield, harsh conditions and cumbersome steps. 6-9 . Therefore, the development of efficient and simple methods for the synthesis of carbonyl α-bor...

Claims

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Application Information

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IPC IPC(8): C07F5/02
CPCC07F5/02
Inventor 吴勇海俐管玫李江联
Owner SICHUAN UNIV
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