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Chirality dihydrogen silane compound and synthetic method and application thereof

A dihydrosilane and compound technology, applied in the field of chiral dihydrosilane compound and its synthesis, can solve problems such as inapplicability and inapplicability of substrates

Active Publication Date: 2017-10-10
ZHEJIANG UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In 2017, Lu group reported the asymmetric hydrosilylation / hydrogenation cascade reaction of alkynes to synthesize chiral silicon compounds, but it is not suitable for aliphatic substrates, and only three-substituted chiral silicon compounds can be synthesized
(Guo, J.; Shen, X.; Lu, Z. Angew. Chem. Int. Ed. 2017, 56, 615.) Subsequently, the Buchwald group reported chiral bisphosphine ligands, copper-catalyzed asymmetric hydrosilation of alkenes , but it needs to use an excess of silane (1.5~5equiv) to react for 12-72 hours, and its chiral disubstituted hydrosilylation product can only be converted into a chiral alcohol compound by Tamao oxidation as an intermediate. In addition, for aliphatic The substrate is also inapplicable

Method used

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  • Chirality dihydrogen silane compound and synthetic method and application thereof
  • Chirality dihydrogen silane compound and synthetic method and application thereof
  • Chirality dihydrogen silane compound and synthetic method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0070] Example 1: Chiral CoX 2 -OIP Complex Catalyzed Hydrosilation of Alkenes and Silanes

[0071] Add chiral CoX to a dry reaction tube at room temperature 2 -OIP complex (0.01mmol), alkene (1.0mmol) shown in formula I, silane (1.0mmol) shown in formula II, ether (2mL), sodium tert-butoxide (0.03mmol), then at room temperature or After stirring at 0° C. for 1 hour, the product was obtained by column chromatography (elution solvent was petroleum ether or a mixture of petroleum ether and ethyl acetate).

[0072]

[0073] In Example 1, chiral CoX 2 The chemical formula of the -OIP complex is as shown in formula III-1:

[0074]

[0075] Preparation Method References: (a) Dai, S.; Sui, X.; Chen, C.Angew.Chem.Int.Ed.2015, 54, 9948-9953. (b) Greenhalgh, M.D.; Thomas, S.P.J.Am. Chem. Soc., 2012, 134, 11900-11903. (c) Leonard, W.R.; Romine, J.L.; Meyers, A.I.J. Org. Chem. 1991, 56, 1961-1963. ; Lu, Z. Org. Lett. 2015, 17, 5939-5941. (e) Guo, J.; Shen, X. Z.; Lu, Z. Angew. ...

Embodiment 2

[0208] Embodiment 2: product oxidation synthesis chiral alcohol compound (application example)

[0209]

[0210] In a 20mL reaction tube, add 1a (0.087g, 0.3mmol), dichloromethane (15mL), stir at 0°C and add HBF 4 ·Et 2 O (0.35g, 1.6mmol, 40%Wt). Stir for 3h, spin off the solvent, then add tetrahydrofuran (3mL), methanol (3mL), potassium fluoride (0.07g, 1.2mmol), potassium bicarbonate (0.30 g, 3.0 mmol), H 2 o 2 (1.5mL, 30%wt). Stir at room temperature for 15h, dilute with water, extract 3 times with ether, wash with saturated brine, dry over anhydrous sodium sulfate, spin dry, pass PE / EtOAc=4 / 1 to get 0.048g (0.24mmol , 81% yield) target product. white solid, [α] 20 D =-42 (c 0.27, CHCl 3 ),99%ee, 1 H NMR (CDCl 3 ,400MHz):δ7.55-7.61(m,4H),7.40-7.47(m,4H),7.31-7.37(m,1H),4.95(q,J=6.4Hz,1H),1.86(br,1H ), 1.54 (d, J=6.4Hz, 3H). (References for experimental procedures: Bergens, S.H.; Noheda, P.; Whelan, J.; Bosnich, B.J.Am.Chem.Soc.1992,114,2121-2128 .Compound data...

Embodiment 3

[0216] Embodiment 3: product oxidation synthesis silanol compound (application example)

[0217]

[0218] 2a (0.1046g, 0.5mmol), BCl was added to the 20mL reaction tube 3 (0.5mmol, 0.5mL, 1.0M inDCM), H 2 O (1.2 mL), dichloromethane (2.0 mL). Stir overnight, dilute with water, extract 3 times with dichloromethane, wash with saturated brine, and dry over anhydrous sodium sulfate. PE / EtOAc=10 / 1 was passed through the column to obtain 0.0790 g (0.35 mmol, 70% yield) of the target product. Oily liquid, 1:1dr. 1 H NMR (CDCl 3 ,400MHz):δ7.45-7.51(m,2H),7.19-7.44(m,12H),7.03-7.15(m,6H),4.93(d,J=1.8Hz,1H),4.90(d,J =2.4Hz, 1H), 2.48-2.57(m, 2H), 2.17(br, 2H), 1.41(d, J=7.8Hz, 3H), 1.38(d, J=7.8Hz, 3H).(compound data Consistent with the literature: Visco, M.D.; Wieting, J.M.; Mattson, A.E.Org. Lett. 2016, 18, 2883-2885.)

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Abstract

The invention discloses a chirality dihydrogen silane compound. The chirality dihydrogen silane compound is as shown in the formula IV. In the formula IV, X represents a chiral carbon atom. The invention further discloses a synthetic method for the chirality dihydrogen silane compound. The method comprises the following steps: using olefin shown in the formula I and silane shown in the formula II as raw materials, and using a chiral CoX2-OIP complex compound as a catalyst, in the existence of a reducing agent, reacting to obtain the chirality dihydrogen silane compound shown in the formula IV. The synthetic method is suitable for different types of the olefins, the reaction condition is moderate, the operation is simple and convenient, and the atomic economy is high. The reaction does not need to be added with any other toxic transition metal ions, the reaction yield is better and is 53%-97% generally, and the enantio-selectivity is higher and is 81%-99% and gt generally. The provided chirality dihydrogen silane compound shown in the formula IV can be used for synthesizing a chiral alcohol compound, a chiral silicon alcohol compound, a chiral polysubstituted silane compound and so on.

Description

technical field [0001] The method relates to a chiral dihydrosilane compound and its synthesis method and application, in particular to a synthesis method of an optically active silane compound. Background technique [0002] Chirality exists widely in nature, and the "thalidomide incident" has made people gradually realize the importance of chirality. Asymmetric catalytic reactions are an important way to prepare chiral compounds. In asymmetric catalytic reactions, metal catalysis is a very important method, but the content of different metals on the earth is different, and some metals have certain toxicity. The asymmetric catalysis of metals is of great significance, especially in the field of medicine and materials, which has broad application prospects. [0003] The hydrosilation reaction is currently widely used to prepare carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-nitrogen double bonds, carbon-nitrogen triple bonds, nitr...

Claims

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Application Information

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IPC IPC(8): C07F7/08C07C33/24C07C33/20C07C33/46C07C33/26C07C31/36C07C31/20C07C29/48C07C43/23C07C41/26C07C321/28C07C319/20C07C69/78C07C67/31C07D333/16C07D333/56C07D213/64C07C49/17C07C45/64
CPCC07B2200/07C07C29/48C07C41/26C07C45/64C07C67/31C07C319/20C07D213/64C07D333/16C07D333/56C07F7/0896C07C33/24C07C33/20C07C33/46C07C33/26C07C31/36C07C31/20C07C43/23C07C321/28C07C69/78C07C49/17
Inventor 陆展程彪
Owner ZHEJIANG UNIV
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