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Catalyst system and catalysis method for catalyzing decarbonylation and hydrogenation of alpha-quaternary carbon aldehyde
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A catalyst and system technology, applied in organic compound/hydride/coordination complex catalysts, chemical instruments and methods, physical/chemical process catalysts, etc.
Active Publication Date: 2022-06-28
SUN YAT SEN UNIV
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[0004]
So far, no efficient catalytic system with good functional group compatibility has been developed for the decarbonylation of large sterically hindered α-quaternary aldehydes, especially for the chirality maintenance of products after decarbonylation of α-chiral quaternary aldehydes more urgent research
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Embodiment 1
[0045] The embodiments of the present application provide a catalytic method for the decarbonylation and hydrogenation of the compound represented by the formula 1-1, which specifically includes:
[0046]
[0047] Take a 25mL Shrek reaction tube and dry it with a high temperature gun, then move it into a glove box, in which [Ir(COD)Cl] 2 (10.3 mg, 0.0153 mmol), L7 (56.9 mg, 0.0603 mmol) and 1-1 (303.8 mg, 1.0013 mmol) were sequentially added to the reaction tube, and finally o-Xylene (1.5 mL) was added. After the temperature was raised to 170°C and reacted for 18 hours, the reaction solution was subjected to direct column chromatography (PE / EA=20:1) to obtain 2-1 ((229.1 mg, 83% yield), pale yellow oil. 1 H NMR (400MHz, CDCl 3 )δ7.32-7.23(m,3H),7.23-7.15(m,1H),7.17-7.09(m,2H),4.06(br.s,2H),2.63(t,J=12.8Hz,2H) , 2.53 (d, J=7.0Hz, 2H), 1.81–1.53 (m, 3H), 1.45 (s, 9H), 1.14 (qd, J=12.6, 4.2Hz, 2H). 13 C NMR (101MHz, CDCl 3 ) δ154.99, 140.36, 129.23, 128.35, 126.05, 79.33, ...
Embodiment 2
[0049] The embodiments of the present application provide a catalytic method for the decarbonylation and hydrogenation of the compound represented by formula 1-2, which specifically includes:
[0050]
[0051] Reference Example 1, [Ir(COD)Cl] 2 (10.2 mg, 0.0152 mmol), L7 (56.8 mg, 0.0602 mmol.), 1-2 (338.2 mg, 1.0023 mmol.), o-Xylene (1.5 mL), and reacted at 170° C. for 18 hours. Column chromatography (PE / EA=10:1) gave 2-2 (290.1 mg, 94%) as a white solid. 1 H NMR (400MHz, CDCl 3 )δ7.41–7.23(m,7H,7.24–7.15(m,1),7.16–7.08(m,2),5.12(s,2),4.16(br.s,2H),2.72(m,2H ), 2.54 (d, J=7.0 Hz, 2H), 1.84–1.53 (m, 3H), 1.25–1.06 (m, 2H). 13 C NMR (101MHz, CDCl 3 )δ155.37,140.17,137.07,129.21,128.56,128.36,128.00,127.92,67.03,44.29,43.18,38.16,31.99. IR(neat): 2926, 2854, 1691, 1240, 1185, 1060cm -1 . MS(EI): m / z(%) 275(M + , 2.97), 57(100). HRMS(ESI + ):m / z calc'd for(M+H) + : 310.1802, found 310.1804. MP: 42.9-43.4°C.
Embodiment 3
[0053] The embodiments of the present application provide a catalytic method for decarbonylation and hydrogenation of compounds represented by formulas 1-3, which specifically include:
[0054]
[0055] Reference Example 1, Ir(COD)Cl] 2 (10.1 mg, 0.0150 mmol.), L7 (56.8 mg, 0.0602 mmol.), 1-3 (308.4 mg, 1.0033 mmol.), o-Xylene (1.5 mL), and reacted at 170° C. for 18 hours. Column chromatography (PE / EA=10:1) gave 2-3 ((270.2 mg, 96% yield). 1 H NMR (400MHz, CDCl 3 )δ7.38(s,5H),7.31–7.26(m,2H),7.23–7.17(m,1H),7.18–7.09(m,2H),4.71(d,J=12.2Hz,1H),3.72 (d, J=13.6Hz, 1H), 3.04–2.62 (m, 2H), 2.57 (t, J=5.6Hz, 2H), 1.99–1.71 (m, 2H), 1.59 (d, J=13.0Hz, 1H), 1.45–0.93 (m, 2H). 13 C NMR (101MHz, CDCl 3 )δ170.31,139.95,136.44,129.44,129.10,128.42,128.34,126.86,126.09,48.05,43.03,42.47,38.37,32.69,31.85. IR(neat): 2916, 2850, 1628, 1431, 1284, 966cm -1 . MS (EI): m / z (%) 279 (M + , 41.45), 105(100). HRMS(ESI + ):m / z calc'd for(M+H) + : 280.1696, found 280.1694.
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Abstract
The invention belongs to the technical field of catalysis of alpha-quaternary carbon aldehyde, and particularly relates to a catalyst system and a catalysis method for catalyzing decarbonylation and hydrogenation of alpha-quaternary carbon aldehyde. The invention provides a catalyst system for catalyzing decarbonylation and hydrogenation of alpha-quaternary carbon aldehyde on the first aspect. The catalyst system is composed of metaliridium and a BIPHEP ligand. The invention provides a method for catalyzing decarbonylation and hydrogenation of alpha-quaternary carbon aldehyde in the second aspect, which comprises the following steps: mixing alpha-quaternary carbon aldehyde with a solvent, and carrying out heating reaction in the presence of a catalyst to obtain a product in which the aldehyde group alpha position corresponding to the alpha-quaternary carbon aldehyde is converted from quaternary carbon into methine and the chiral carbon configuration is maintained, the catalyst is composed of metaliridium and a BIPHEP ligand. The catalyst system and the catalytic method provided by the invention can effectively solve the problem that an efficient catalytic method for decarbonylation hydrogenation of large-steric-hindrance alpha-quaternary aldehyde with good functional group compatibility does not exist in the prior art.
Description
technical field [0001] The application belongs to the technical field of organic synthesis catalyzed by transition metals, and in particular relates to a catalyst system and a catalytic method for catalyzing the dehydrogenation of α-quaternary aldehydes. Background technique [0002] Aldehyde compounds are an important class of compounds, which are one of the readily available bulk chemicals and also have good application prospects in the fields of medicine, food and feed. Aldehyde is also a kind of active functional group, which can undergo various chemical reactions: oxidation, reduction, coupling, condensation and addition reactions; at the same time, the interaction of aldehyde group or aldehyde group with amine (in situ formation of imine) can be used as a guiding group , under the condition of metalcatalysis, transformations such as directed fluorination, amination, boronation, alkylation, and arylation can be realized. Therefore, it is of great significance to devel...
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