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Chiral geminal disilicide alkane compound containing four silicon-hydrogen bonds as well as synthesis method and application thereof

A technology of disilazane and compound, applied in the field of chiral gem disilazane compound containing four silicon-hydrogen bonds and its synthesis and application

Active Publication Date: 2019-03-22
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] Therefore, the preparation of chiral gem-disilazane compounds containing four silicon-hydrogen bonds via inexpensive metal-catalyzed tandem hydrosilylation of alkynes or asymmetric hydrosilylation of alkenylsilicones is a significant challenge.

Method used

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  • Chiral geminal disilicide alkane compound containing four silicon-hydrogen bonds as well as synthesis method and application thereof
  • Chiral geminal disilicide alkane compound containing four silicon-hydrogen bonds as well as synthesis method and application thereof
  • Chiral geminal disilicide alkane compound containing four silicon-hydrogen bonds as well as synthesis method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0086] Example 1: Chiral CoX 2 Asymmetric Hydrosilylation of Alkenyl Silicon and Silane Catalyzed by -IIP Complex

[0087] Add chiral CoX sequentially to a dry reaction tube at room temperature under argon 2 -IIP complex (0.015mol, 3mol%), toluene (2.0mL), trihydrosilane (0.55mmol) shown in formula IV, sodium triethylborohydride (0.045mol, 9mol%), shown in formula V alkenyl silicon (0.5 mmol). 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 reaction conditions, chiral CoX 2 The amounts of -IIP complex and sodium triethylborohydride varied and are specified under each product. )

[0088]

[0089] VI-1:

[0090] (R)-Benzyl(1-(phenylsilyl)hexyl)silane

[0091] (R)-benzyl(1-(phenylsilyl)hexyl)silane

[0092]

[0093] Oily liquid, 83% yield, regioselectivity >19 / 1, [α] 20 D =-8.3 (c 1.02, CHCl 3 ),98.8%ee, IR(cm ...

Embodiment 2

[0128] Example 2: Chiral CoX 2 Asymmetric hydrosilylation of alkynes and two different trihydrosilanes catalyzed by -IIP complex

[0129] Add Co(OAc) sequentially to a dry reaction tube at room temperature under argon 2 (0.01mmol), Dpephoes (0.012mmol), toluene (2.0mL), trihydrosilane (0.50mmol) shown in formula II, sodium triethylborohydride (0.03mol), alkyne (0.50mmol) shown in formula I mmol), stirred at room temperature for 3 hours. Then, under the protection of argon, add CoX 2 -IIP (0.015mol), trihydrosilane (0.50mmol) shown in formula VI, sodium triethylborohydride (0.045mol) was stirred at room temperature for 3 hours and separated by column chromatography (elution solvent is sherwood oil or sherwood oil and ethyl acetate) to give the product.

[0130]

[0131] In Example 2, chiral CoX 2 The chemical formula of the -IIP complex is shown in the following formula III-1:

[0132]

[0133] The preparation method is the same as described in Implementation 1.

[0...

Embodiment 3

[0156] Embodiment 3: product oxidation synthesis aldehyde compound (application example)

[0157]

[0158] In a 20mL reaction tube, add VI (1.0mmol), chloroform (5mL), HBF 4 .OEt 2 (6mmol, 40%Wt), the mixture was refluxed for 24 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 (50mmol, 30%wt).Stir at room temperature for 10h, 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. )

[0159] The following products were oxidized into aldehyde compounds with reference to the above method, as shown in Table 1.

[0160] Table 1 Oxidative synthesis of aldehydes from chiral gem-disilazane products

[0161] ...

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Abstract

The invention discloses a chiral geminal disilicide alkane compound containing four silicon-hydrogen bonds, shown as a formula VI, and discloses a synthesis method of the chiral geminal disilicide alkane compound. For the first method, in inert gas, a vinyl silane type compound shown as a formula V and silane trihydride shown as a formula IV are used as raw materials; a chiral CoX2-IIP complex compound is used as a catalyst; under the existence of reducing agents, reaction is performed to prepare VI. For the second method, in the inert gas, alkyne shown as a formula I, silane trihydride shownas a formula II and silane trihydride shown as a formula IV are used as raw materials; CoY2, bi(2-diphenyl phosphenyl) ether and a chiral CoX2-IIP complex compound are used as catalysts; under the existence of reducing agents, reaction is performed to prepare a formula VI. The method has the advantages of mild reaction conditions, operation simplicity and convenience, high atom economy, excellentproductive rate (57 to 84 percent), high regioselectivity (greater than 19:1) and high enantioselectivity (91.6 to 98.8 percent ee). The formulas are shown in description.

Description

technical field [0001] The method relates to a chiral gem-disilazane compound containing four silicon-hydrogen bonds and its synthesis method and application. Background technique [0002] Chiral organosilanes in organic synthesis [(a) Masse, C.E.; Panek, J.S.Chem.Rev.1995, 95, 1293. (b) Fleming, I.; Barbero, A.; , 97, 2063. (c) Brook, M.A. Siliconin Organic, Organometallic and Polymer Chemistry, Wiley, New York, 2000. (d) Zhang, H.-J.; Priebbenow, D.L.; Bolm, C.Chem.Soc.Rev .2013,42,8540.] and functional materials [(a) Ojima, I.In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; Wiley:Chichester,1989; Vol.1, Chapter 25. (b) Silicon in Organic, Organometallic, and Polymer Chemistry; Brook, M.A., Ed.; Wiley: New York, 1999. (c) Ponomarenko, S.A.; Kirchmeyer, S. Adv Polym Sci. 2011, 235, 33 .] and other fields have important applications. Gem disilazanes, that is, compounds with two silicon groups attached to the same carbon of the alkyl group, on...

Claims

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Application Information

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IPC IPC(8): C07F7/08C07C45/27C07C47/02C07C47/14
CPCC07C45/27C07F7/0812C07F7/0829C07C47/02C07C47/14
Inventor 陆展程朝阳郭军
Owner ZHEJIANG UNIV
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