A method for catalytic asymmetric synthesis of binaphthyl diamines
A technology of binaphthyldiamine and compounds, which is applied in the field of catalytic asymmetric synthesis of binaphthyldiamine, which can solve the problems of substrate light and thermal instability, redox potential difference, and small application range of substrates.
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Embodiment 1
[0055] Synthesis of substrates
[0056] Azonaphthalene derivative 1 (compound A) can be obtained through literature Qi, L.-W.; Mao, J.-H.; Zhang, J.; Tan, B. Nat. Chem.2018,10,58-64. Synthesized by the disclosed method.
[0057] Substituted 2-naphthylamine 2 (compound B) can be obtained by literature Chen, Y.-H.; Qi, L.-W.; Fang, F.; Tan, B.Angew. Chem.Int.Ed.2017,56 , 16308-16312. Synthesized by the method disclosed.
[0058] Substrate 4a is commercially available.
[0059] Substrates 4n and 4o can be obtained through the literature Majumdar, K.C.; Samanta, S.; Chattopadhyay, B.; Nandi, R.K. Synthesis 2010, 2010, 863-869., Chen Y.; Dubrovskiy, A.; . 2012, 89, 294-306. Synthesized by the method disclosed.
[0060]
[0061] To a DCM solution (10 mL) of 2-naphthylamine H (1.0 mmol), benzaldehyde J (1.0 mmol) and compound K (0.38 g, 1.5 mmol) was added AcOH (86 μL, 1.5 mmol), and the mixture was heated at room temperature Stir. After completion of the reaction (monitored...
Embodiment 2
[0099] Except for L10, all BOX (bisoxazoline) ligands used in the present invention are known compounds (synthesized with reference to the following documents: Honma, M.; Sawada, T.; Fujisawa, Y.; Utsugi, M.; Watanabe, H.; Umino, A.; Matsumura, T.; Hagihara, T.; Takano, M.; , L.; Zhong, J.-C., Z.; Yun, Z.; Gao, Z.-D.; Bing, Q.-H. Chem.-Eur.J.2018,24,2059-2064. , Liu, Q.-J.; Wang, L.; Kang, Q.-K.; Zhang, X.P.; Tang, Y. Angew. Chem. Int. Ed.2016, 55, 9220-9223. .; Sheng, Z.; Yu, W.; Wu, G.; Zhang, R.; Chu, W.-D.; ., Xiong, H.; Xu, H.; Liao, S.; Xie, Z.; Tang, Y.J.Am.Chem.Soc.2013, 135, 7851-7854.). L1 can be purchased from commercial sources.
[0100] Synthesis of L10
[0101]
[0102] To a stirred solution of malononitrile (0.26 g, 3.86 mmol), 3,5-dimethoxybenzyl bromide (1.96 g, 2.2 eq) in DMF (20 mL) was added DBU (1.29 g, 2.2 eq) . The mixture was heated to 80°C and stirred for 2 hours. After cooling to room temperature, water (50 mL) and DCM (50 mL) were added seq...
Embodiment 3
[0106] Optimization of reaction conditions
[0107] Reactions were performed on a 0.1 mmol scale in 2 mL of solvent at room temperature, unless otherwise stated, in a 1:1.2 ratio of 1a:4a.
[0108]
[0109]
[0110]
[0111] a: use 4mL CHCl 3 ; b: 5 mol% catalyst was used; c: the reaction was carried out at 0°C.
[0112] Characterization data for 5a:
[0113] 1 H NMR (500MHz, DMSO-d 6 )δ9.27(s,1H),7.98(d,J=8.9Hz,1H),7.87(d,J=7.9Hz,1H),7.82(d,J=8.9Hz,1H),7.75(d, J=7.6Hz, 1H), 7.38(d, J= 8.8Hz, 1H), 7.25–7.12(m, 10H), 6.82(dd, J=22.8, 7.8Hz, 2H), 6.18(s, 1H), 4.84(s,1H),4.45-4.35(m,2H),3.58(s,3H). 13 C NMR (125MHz, DMSO-d 6 )δ157.9,145.7,144.6,140.7,134.0,133.6,129.8,129.2,128.7(3C),128.6,128.4,127.4,127.3(2C),127.0,126.9,126.7,124.1,123.9,11141.8,123.9,1 , 112.5, 110.7, 52.4, 47.0. HRMS (ESI) accurate mass calculation [M+H] C 29 h 26 N 3 o 2 , m / z: 448.2020, measured value: 448.2011. HPLC analysis: HPLCDAICEL CHIRALCEL IB n-hexane / isopropanol=80 / 20, 1.0mL...
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