Method for synthesizing 3-coumarin compound containing chiral tertiary alcohol structure
A technology for coumarinone and compound, which is applied in the field of organic synthesis, can solve problems such as few studies, and achieve the effect of maintaining stereoselectivity
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[0077] The present invention relates to the preparation of the above-mentioned chiral copper complex catalyst, and its preparation method comprises: divalent copper salt (also referred to as copper salt sometimes), nitrogen-containing organic base and the ligand of formula (L1) or (L2) in a solvent Mixing reaction in the medium to obtain the chiral copper complex catalyst of formula (C1) or (C2).
[0078] In some embodiments, the ligand is selected from:
[0079]
[0080] In some embodiments, the divalent copper salt is selected from copper bromide, copper fluoride, copper chloride, copper trifluoromethanesulfonate, copper nitrate, copper sulfate, copper acetate, and the like.
[0081] In some embodiments, the nitrogen-containing organic base is selected from triethylenediamine, triethylamine, piperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N- Diisopropylethylamine, N-ethylmorpholine, etc.
[0082] In the presence of the prepared chiral copper complex catalyst, the 3-co...
Embodiment 1
[0097] Embodiment 1 (condition optimization)
[0098] 1.1 prepare chiral copper complex catalyst, described chiral copper complex is made of copper bromide, triethylenediamine and ligand L 1 It is prepared by stirring in ethanol at room temperature for 2 hours at a molar ratio of 1:1:1.
[0099] 1.2 3-coumaranone compounds and β, γ unsaturated ketone ester compounds shown in above-mentioned formula (I) are added respectively in the above-mentioned prepared catalyst, catalyst and reactant β, γ unsaturated ketone ester compound The molar ratio is 1:10; the amount of solvent ethanol is such that the initial concentration of β, γ unsaturated ketone esters is 0.1mol / L.
[0100] 1.3 Extract the reacted solution with ethyl acetate, back-extract with saturated saline, dry over anhydrous sodium sulfate, spin dry, and pass the residue through the column with silica gel, using petroleum ether / ethyl acetate system as the eluent from the volume ratio 10 / 1-2 / 1 column; the eluent selected ...
Embodiment 2
[0116] Add copper bromide (2.2mg, 0.01mmol) successively in a 10mL reaction tube, ligand (L 1 , 4.3mg, 0.01mmol), ethanol (1.0mL), triethylenediamine (1.1mg, 0.01mmol) and stirred at room temperature for 2h. Then, 3-coumaranone 1a (20.1mg, 0.15mmol) and β, γ unsaturated ketoester 2a (21.8mg, 0.1mmol) were added sequentially at -15°C. After the reaction was completed (TLC tracking detection), use Extracted with ethyl acetate, extracted with saturated brine, dried over anhydrous sodium sulfate, and spin-dried the obtained residue to pass through the column with petroleum ether / ethyl acetate system as eluent to obtain yellow oily liquid (S, R)-3a (93% Yield, 32.7 mg, 94% / 95% ee).
[0117] Utilize nuclear magnetic resonance (Bruker AC-300FT) to analyze the target product (S, R)-3a obtained in embodiment 2, obtain its proton nuclear magnetic resonance spectrum, as figure 1 shown. 1 H NMR (400MHz, CDCl 3 ): δ7.67(d, J=7.1Hz, 1H), 7.63–7.57(m, 1H), 7.48(d, J=7.3Hz, 2H), 7.35(t, J...
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