Chiral spiro phosphoric acid dirhodium complex as well as preparation method and application thereof

A technology of spirocyclic phosphoric acid and rhodium complexes, which is applied in the direction of rhodium organic compounds, organic compound/hydride/coordination complex catalysts, silicon organic compounds, etc., which can solve the problem of small differences in steric hindrance and difficulty in obtaining high enantioselectivity , Reaction type limitations and other issues, to achieve the effect of high activity

Pending Publication Date: 2020-09-04
ZHEJIANG JIUZHOU PHARM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the research of this type of reaction mainly focuses on carbene with electron-withdrawing substituents (ester group, amide, cyano group, etc.), which leads to the limitation of reaction types and the single structure of insertion products [Keipour, H.; Carreras, V.; Ollevier, T. Org. Biomol. Chem. 2017, 15, 5441.]
However, the asymmetric silicon-hydrogen b

Method used

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  • Chiral spiro phosphoric acid dirhodium complex as well as preparation method and application thereof
  • Chiral spiro phosphoric acid dirhodium complex as well as preparation method and application thereof
  • Chiral spiro phosphoric acid dirhodium complex as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Synthesis of (S)-5,5'-bis(pinacol borate)-7,7'-bis(methoxy)-1,1'-spirobisdihydroindene (2a)

[0030]

[0031] Add compound 1 (2.3g, 8.0mmol), double pinacol borate (B 2 pin 2 , 4.5g, 17.6mmol), [Ir(OMe)(cod)] 2(212mg, 0.32mmol), and the ligand (151mg, 0.64mmol). The system was replaced by an argon atmosphere, dry tetrahydrofuran (30 mL) was added with a syringe, and stirred evenly. The oil bath was heated to 80° C. to react for 8 hours, and the reaction was complete as monitored by TLC. Cool to room temperature, remove the solvent with a rotary evaporator, and the residue is subjected to silica gel column chromatography (dichloromethane) to obtain 3.8 g of crude product, with a crude yield of 90%. Heating and recrystallization in redistilled petroleum ether gives pure White solid 2a, yield 70%, melting point: 190-192°C, [α] D 25 =-34.0 (c 1.0, CHCl 3 ).

[0032] 1 H NMR (400MHz, CDCl 3 )

[0033] δ7.34(s, 2H, ArH), 7.04(s, 2H, ArH), 3.56(s, 6H, 2OCH 3 ...

Embodiment 2

[0041] Synthesis of (S)-5,5'-diphenyl-7,7'-bis(methoxy)-1,1'-spirobisdihydroindene (3a)

[0042]

[0043] Add compound 2a (1.3g, 2.5mmol), bromobenzene (PhBr, 2.36g, 15.0mmol) and tetrakistriphenylphosphine palladium (Pd(PPh 3 ) 4 , 443mg, 0.375mmol), after replacing argon, add toluene (30mL), ethanol (14mL) and potassium carbonate aqueous solution (1N, 20mL) successively, freeze and degas, and then place the reaction system in a 90°C oil bath to heat Stir overnight. After the completion of the reaction as monitored by TLC, cool to room temperature and dilute with ethyl acetate, separate the layers, extract the aqueous phase with ethyl acetate (3×20 mL), combine the organic phases and wash with saturated brine, and dry over anhydrous magnesium sulfate. After suction filtration and precipitation, silica gel column chromatography (petroleum ether / dichloromethane=4:1) gave 0.8 g of white solid 3a, yield 78%, melting point: 58-60 °C, [α] D 25 =-1.4 (c 1.0, CHCl 3 ).

[00...

Embodiment 3

[0051] Synthesis of (S)-5,5'-diphenyl-1,1'-spirobisdihydroindane-7,7'-diol (4a)

[0052]

[0053] Compound 3a (0.85 g, 2.0 mmol) was added into a 250 mL dry three-neck flask equipped with magnetic stirring, replaced with an argon atmosphere, dry dichloromethane (20 mL) was added with a syringe, and stirred evenly. The system was cooled to -78°C, and a solution of boron tribromide in dichloromethane (BBr 3 , 1M, 15mL), naturally return to room temperature, and stir overnight. The completion of the reaction was monitored by TLC, dichloromethane was added to dilute the reaction system, the organic phases were combined, washed successively with saturated sodium bisulfite solution, saturated sodium bicarbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. Suction filtration, precipitation, and silica gel column chromatography (petroleum ether / dichloromethane = 1:1) yielded 0.46 g of white solid 4a, yield 57%, melting point: 101-102°C. [α] D 25 =+4...

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Abstract

The invention relates to a chiral spiro phosphoric acid dirhodium complex as well as a preparation method and application thereof. The chiral spiro phosphoric acid dirhodium complex is a compound shown in a formula I, can be prepared by reacting phosphoric acid with a chiral spiro indane skeleton with rhodium acetate, and is mainly structurally characterized in that four chiral spiro phosphoric acid anions are coordinated to two rhodium atoms. The complex can catalyze the insertion reaction of carbene derived from diaryldiazo to a silicon-hydrogen bond to prepare a chiral organosilicon compound.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a chiral spirocyclic dirhodium phosphate complex and its preparation method and application, in particular to the preparation of a class of chiral spirocyclic dirhodium phosphate complexes with a spirobidihydroindane skeleton Method and its application in the asymmetric intercalation reaction of carbene to silicon-hydrogen bond. Background technique [0002] A pair of enantiomers of chiral compounds usually exhibit different biological activities, thus selectively obtaining chiral compounds of a single configuration has become a common concern of synthetic chemists [Nicolaou, K.C.; Montagnon, T.Molecules that Changed the World; Wiley-VCH, 2008]. Asymmetric catalytic synthesis has become one of the most effective methods to obtain chiral compounds because of its advantages of chiral proliferation and high efficiency [Jacobsen, E.N.; Pfaltz, A.; Yamamoto, H.Comprehensive A...

Claims

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Application Information

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IPC IPC(8): C07F15/00B01J31/22C07F7/08C07F7/10
CPCC07F15/008B01J31/2213C07F7/0805C07F7/081C07F7/0812C07F7/0827C07B2200/07B01J2531/822B01J2531/0219
Inventor 周其林朱守非杨亮亮王立新
Owner ZHEJIANG JIUZHOU PHARM CO LTD
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