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Preparation method and application of a class of chiral six-membered nitrogen heterocyclic carbene precursor salt
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A nitrogen-heterocyclic carbene and chiral technology, which is applied in the field of synthesis of chiral six-membered nitrogen-heterocyclic carbene precursor salts, can solve the problems of low total yield and many synthesis steps
Inactive Publication Date: 2019-11-22
ZHEJIANG UNIV CITY COLLEGE
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Abstract
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Problems solved by technology
However, most of the existing chiral six-membered nitrogen-heterocyclic carbenes have many synthesis steps and low overall yields.
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Embodiment 1
[0068] Preparation and characterization of compound Ⅲ-1:
[0069]
[0070] Add 548.7 mg (4 mmol) of compound Ⅰ-1 and 204 μL of 1,3-dibromopropane into the reaction tube, and react using General Method 1, and react at 100 ° C for 12 hours. NaOH solution (40mL) was dissolved, extracted with dichloromethane (15mL) three times, the organic phase was combined, the organic phase was washed with saturated brine, and anhydrous Na 2 SO 4 Dry, filter, and the filtrate is spin-dried to obtain yellow oil II-1. Add II-1 (2 mmol), 333 μL triethyl orthoformate, and 210 mg ammonium tetrafluoroborate into the reaction tube, and stir at 120° C. for 4 hours. After the reaction, the mixture was separated by column chromatography (CH 2 Cl 2 :CH 3 OH=80:1~40:1) A total of 689 mg of product III-1 was obtained as a light yellow oily compound with a yield of 84%; 1 HNMR (500MHz, CDCl 3 ):δ8.58(s,1H),7.39–7.34(m,5H),7.30(m,5H),4.93(dd,J=9.8,3.4Hz,2H),4.24–4.17(m,2H), 4.09(d,J=11.0Hz,2H),3.28–...
Embodiment 2
[0072] Preparation and characterization of compound Ⅲ-2:
[0073]
[0074] The preparation conditions were the same as in Example 1, the yellow oily compound had a yield of 86%; 1 H NMR (500MHz, CDCl 3 ):δ7.97(s,1H),3.96(dd,J=12.5,3.7Hz,2H),3.68(dd,J=12.4,9.4Hz,2H),3.48–3.37(m,4H),3.30( m,2H),2.19–2.15(m,2H),1.96–1.89(m,2H),1.02(d,J=6.6Hz,6H),0.97(d,J=6.6Hz,6H); 13 C NMR (125MHz, CDCl 3 ): δ154.05, 59.75, 40.72, 29.72, 27.29, 19.75, 19.37; HR-ESIMS: m / z 257.2229 [M-BF 4 ] + (calcd for C 14 h 29 N 2 o 2 + , 257.2224).
Embodiment 3
[0076] Preparation and characterization of compound Ⅲ-3:
[0077]
[0078] The preparation conditions were the same as in Example 1, the yellow oily compound had a yield of 92%; 1 HNMR (500MHz, CDCl 3 ):δ7.94(s,1H),3.95(dd,J=12.4,3.7Hz,2H),3.68(dd,J=12.2,9.4Hz,2H),3.46–3.35(m,6H),2.21– 2.13(m,2H),1.73(m,2H),1.41(m,2H),1.14(m,2H),0.97(d,J=6.6Hz,6H),0.91(t,J=7.4Hz,6H ); 13 C NMR (125MHz, CDCl 3 ): δ154.00, 71.78, 59.74, 41.04, 33.20, 25.54, 18.79, 15.22, 10.38; HR-ESIMS: m / z 285.2796 [M-BF 4 ] + (calcd for C 16 h 33 N 2 o 2 + , 285.2537).
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Abstract
The invention relates to the field of organic synthesis, in particular to synthesis and application of chiral hexahydric n-heterocyclic carbene precursor salt with a tetrahydropyrimidine skeleton. A chiral hexahydric n-heterocyclic carbene precursor compound is a compound with the structure as shown in the formula (III) or an enantiomer as shown in the formula (III'), and the formulas (III and III') are as shown in the description, wherein R1 is selected from phenyl, 1-naphthyl, 2-naphthyl, benzyl, isopropyl, isobutyl, sec-butyl, tert-butyl or cyclohexyl; R2 is selected from chloride ion, bromide ion, tetrafluoroborate ion or hexafluorophosphate ion and is preferably selected from chloride ion and tetrafluoroborate ion; and R3 is selected from hydrogen, 1-naphthoyl, 2-naphthoyl, 2,4,6-trimethylbenzoyl, methoxybenzoyl or tert-butylbenzoyl. According to a synthetic method of the C2-symmetric novel chiral hexahydric n-heterocyclic carbene precursor compound, and the application range of the C2-symmetric novel chiral hexahydric n-heterocyclic carbene precursor compound to drug intermediate synthesis and asymmetric organic synthesis reactions is expanded.
Description
technical field [0001] The invention relates to the field of organic synthesis, in particular to the synthesis and application of a chiral six-membered nitrogen heterocyclic carbene precursor salt with a tetrahydropyrimidine skeleton. Background technique [0002] The research on nitrogen-heterocyclic carbene (NHCs) began in the 1970s. Until 1991, after Arduengo et al. prepared free nitrogen-heterocyclic carbene monomers for the first time, carbene chemistry developed by leaps and bounds. Nitrocyclic carbene has attracted more and more attention due to its advantages such as relatively simple preparation and less harsh requirements on the reaction environment. In addition, the strong σ-donating and weak π-accepting properties of nitrogen heterocyclic carbene enable it to form stable metal complexes with most metals, and exhibit better air and thermodynamic stability, so that such complexes can Catalyze many important organic chemical reactions, such as olefin metathesis rea...
Claims
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