Racemic gem disilyl alkane compound containing four silicon-hydrogen bonds, and sybthesis method and application of compound

A technology for disilyl alkane and compound, which is applied in the field of external elimination of gem-disil alkane compound and its synthesis, and can solve the problems of difficult regulation of reaction area and chemical selectivity, etc.

Active Publication Date: 2019-05-03
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the reaction has difficulties such as reaction area and difficult control of chemoselectivity, and it is very challenging to synthesize polysilicon compounds through tandem hydrosilation of alkynes.

Method used

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  • Racemic gem disilyl alkane compound containing four silicon-hydrogen bonds, and sybthesis method and application of compound
  • Racemic gem disilyl alkane compound containing four silicon-hydrogen bonds, and sybthesis method and application of compound
  • Racemic gem disilyl alkane compound containing four silicon-hydrogen bonds, and sybthesis method and application of compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0063] Example 1: Chiral CoX 2 Tandem hydrosilation of alkynes and silanes catalyzed by -IIP complexes

[0064] Add chiral CoX sequentially to a dry reaction tube at room temperature under argon 2 -IIP complex (0.015mol, 3mol%), toluene (2.0mL), trihydrosilane (1.1mmol) shown in formula II, sodium triethylborohydride (0.045mol, 9mol%), shown in formula I Alkyne (0.5mmol). After stirring at room temperature for 2 hours, the product was obtained by column chromatography (elution solvent was petroleum ether or a mixture of petroleum ether and ethyl acetate). (In individual reactions, chiral CoX 2 - The amounts of IIP complex and sodium triethylborohydride vary and are specified under each product)

[0065]

[0066] In Example 1, chiral CoX 2 The chemical formula of the -IIP complex is shown in the following formula III-1:

[0067]

[0068] The specific preparation method is as follows:

[0069]

[0070] Under nitrogen protection, palladium acetate (0.0576g, 0.26mm...

Embodiment 2

[0263] Embodiment 2: product oxidation synthesis aldehyde compound (application example)

[0264]

[0265] In a 20mL reaction tube, add IV (1.0mmol), chloroform (5mL), HBF 4 .OEt 2 (6mmol, 40%Wt), the mixture was refluxed for 12 hours, the solvent was spun off, and then tetrahydrofuran (1mL), methanol (3mL), tetrabutylammonium fluoride (8.0mmol), potassium bicarbonate (8.0mmol) were added in sequence ,H 2 o 2 (40mmol, 30%wt).Stir at room temperature for 2h, saturated NaHSO 3 The solution was diluted, extracted three times with ether, washed with saturated brine, dried over anhydrous sodium sulfate, spin-dried, and passed through a column with PE / EtOAc=20 / 1 to obtain compound A (reference for experimental procedures: Chem.Commun.2002, 114-115. )

[0266] The following products were oxidized into aldehyde compounds with reference to the above method, as shown in Table 1.

[0267] Table 1 Synthesis of aldehydes by oxidation of racemic disilazane products

[0268]

[...

Embodiment 3

[0271] Embodiment 3: product synthesis polysubstituted silane compound (application example)

[0272]

[0273] Under the protection of argon, add Xantphos.CoCl to a dry 25mL reaction tube successively 2 (0.0178g, 0.025mmol), toluene (5.0mL), IV-1 (0.0747g, 0.25mmol), sodium triethylborohydride (75μL, 1.0M, 0.075mmol), B-1 (115μL, 0.72g / mL, 1.0 mmol), reacted at room temperature for 36 hours, and passed through the PE column to obtain the target product C-1 (0.0804 g, 0.17 mmol, 69% yield), an oily liquid. IR (cm -1 ):3067,2957,2925,2855,2113,1614,1462,1429,1168; 1 H NMR (400MHz, CDCl 3 ):δ7.55-7.45(m,4H),7.39-7.27(m,6H),6.26-6.13(m,2H),5.75-5.61(m,2H),4.60-4.52(m,2H),2.17 -2.06(m,4H),1.56-1.47(m,2H),1.40-1.24(m,10H),1.20-1.04(m,4H),0.92-0.86(m,6H),0.82-0.75(m, 3H),0.67-0.59(m,1H); HRMS(EI) calculated for [C 30 h 46 Si 2 ] + requires m / z 462.3138, found m / z 462.3137.

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Abstract

The invention discloses a racemic gem disilyl alkane compound containing four silicon-hydrogen bonds. The compound is as shown in a formula IV. The invention further discloses a synthesis method of the racemic gem disilyl alkane compound. The synthesis method comprises the following step of carrying out a reaction by taking alkyne as shown in a formula I and trihydrosilane as shown in a formula IIas raw materials and taking a chiral CoX<2>-IIP complex as a catalyst in the presence of a reducing agent to obtain the racemic gem disilyl alkane compound containing four silicon-hydrogen bonds, wherein the compound is as shown in the formula IV. The method disclosed by the invention has mild reaction conditions, is simple and convenient to operate and has high atom economy. In addition, the reaction does not need addition of any salts of toxic transition metals (such as ruthenium, rhodium, palladium and the like), and the method has a relatively large practical application value in synthesis of medicines and materials. In addition, the reaction has a medium to excellent yield (51-99%) and high area selectivity (10:1-19:1, most parts larger than 19:1).

Description

technical field [0001] The method relates to a racemic disilazane compound containing four silicon-hydrogen bonds and its synthesis method and application. Background technique [0002] Organoalkylsilicon compounds in organic synthesis [(a) Fleming, I.; Barbero, A.; Walter, D.Chem.Rev.1997, 97, 2063. (b) Denmark, S.E.; Regens, C.S.Acc.Chem. Res.2008,41,1486.(c) Nakao,Y.; Hiyama,T.Chem.Soc.Rev.2011,40,4893.(d)Jensen,K.L.;Dickmeiss,G.;Jiang,H.;Albrecht , K.A.Acc.Chem.Res.2012,45,248.(e) Zhang,H.-J.; Priebbenow,D.L.; Bolm,C.Chem.Soc.Rev.2013,42,8540.] Organometallic, and Polymer Chemistry; Brook, M.A., Ed.; Wiley: New York, 1999.], and medicinal chemistry [(a) Pooni, P.K.; Showell, G.A. Mini-Rev. Med. Chem. 2006, 6, 1169. (b) Gately, S.; West, R. Drug Dev. Res. 2007, 68, 156. (c) Franz, A.K.; Wilson, S.O.J. Med. Chem. 2013, 56, 388. (d) Min, G.K.; Hernández, D. ; Skrydstrup, T.Acc.Chem.Res.2013,46,457.] and other fields have many applications. Gem disilazanes, that is, ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/08C07F7/18C07F7/12C07F7/10C07C45/28C07C47/02C07C47/11C07C47/23C07D333/22C07C231/12C07C235/74
Inventor 陆展程朝阳邢世沛郭军
Owner ZHEJIANG UNIV
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