JP5334252B2 - 光学活性フェニルビスイミダゾリン−遷移金属錯体触媒およびそれを用いて高エナンチオ選択的に生成物を得る方法 - Google Patents
光学活性フェニルビスイミダゾリン−遷移金属錯体触媒およびそれを用いて高エナンチオ選択的に生成物を得る方法 Download PDFInfo
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- JP5334252B2 JP5334252B2 JP2009034366A JP2009034366A JP5334252B2 JP 5334252 B2 JP5334252 B2 JP 5334252B2 JP 2009034366 A JP2009034366 A JP 2009034366A JP 2009034366 A JP2009034366 A JP 2009034366A JP 5334252 B2 JP5334252 B2 JP 5334252B2
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- transition metal
- phenylbisimidazoline
- optically active
- metal complex
- phebim
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Description
下記化学式2で示される[Phebim]Brの合成
分子式 : C36H29BrN4 M.W. : 597.55
Rf = 0.32 (ジクロロメタン/メタノール9:1)
1H NMR (200 MHz, CDCl3): 7.68 (d, J = 7.8 Hz, 2H, Ar), 7.43-7.18 (m, 21H, Ar), 5.94 (br, 2H, NH), 4.80 (s, 4H, CH).
IR (KBr): 3391, 3060, 3028, 2908, 1707, 1619, 1577, 1493, 1452, 1279, 1191, 1030, 1006, 761, 698 cm-1
分子式 : C50H41BrN4O4S2 M.W. : 905.92 Rf = 0.47 (ヘキサン/酢酸エチル6:4)
1H NMR(200 MHz, CDCl3) δ 7.80-6.95 (br, 31H, Ar), 5.16 (br, 4H, CH), 2.40 (s, 6H, CH3).
IR (KBr): 3062, 3030, 2923, 1640, 1597, 1495, 1455, 1365, 1169, 1135, 1092, 803, 760, 698, 666 cm-1
分子式 : C50H41BrN4O4PdS2 M.W. : 1012.34 Rf = 0.34 (ジクロロメタン)
1H NMR (200 MHz, CDCl3) 8.68 (d, J = 8.2 Hz, 2H, Ar), 7.50-7.00 (m, 25H, Ar), 6.79 (d, J = 6.6 Hz, 4H, Ar) 5.31 (d, J = 3.0 Hz, 2H, CH), 5.19 (d, J = 3.0 Hz, 2H, CH), 2.40 (s, 6H, CH3).
IR (KBr): 3062, 3031, 1594, 1569, 1523, 1494, 1455, 1370, 1172, 1092, 1024, 997, 812, 754, 698, 681, 665 cm-1
分子式 : C50H41BrN4NiO4S2 M.W. : 964.61 Rf = 0.13 (酢酸エチル/ヘキサン 1:1)
1H NMR (200 MHz, CDCl3) 8.57 (d, J = 7.8 Hz, 2H, Ar), 7.51-7.00 (m, 25H, Ar), 6.79 (d, J = 6.6 Hz, 4H, Ar), 5.19 (d, J = 2.4 Hz, 2H, CH), 5.03 (d, J = 2.4 Hz, 2H, CH), 2.40 (s, 6H, CH3).
IR (KBr): 2925, 2852, 1457, 1376, 1173, 1092, 1025, 812, 756, 698, 665 cm-1
分子式 : C50H37BrN4O2 M.W. : 805.76 Rf = 0.23 (ヘキサン/酢酸エチル1:1)
1H NMR(200 MHz, CDCl3) 7.48-6.94 (m, 33H, Ar), 5.30 (d, J = 7.8 Hz, 2H, CH), 5.23 (d, J = 7.8 Hz, 2H, CH).
IR (KBr): 3061, 3030, 2924, 1672, 1633, 1581, 1494, 1449, 1337, 1180, 1146, 757, 697 cm-1
下記化学式7で示される[PhCO-Phebim]PdBrの合成
分子式 : C50H37BrN4O2Pd M.W. : 912.18 Rf = 0.30 (酢酸エチル/ヘキサン 6:4)
1H NMR (200 MHz, CDCl3) 7.69 (d, J = 7.8 Hz, 2H, Ar), 7.50-7.02 (m, 31H, Ar), 5.22 (d, J = 2.4 Hz, 2H, CH), 5.13 (d, J = 2.4 Hz, 2H, CH).
IR (KBr): 3062, 3031, 1685, 1570, 1455, 1374, 1319, 1161, 1022, 758, 731, 696 cm-1
分子式 : C50H37BrN4NiO2 M.W. : 862.15 Rf = 0.47 (酢酸エチル/ヘキサン 1:1)
1H NMR(200 MHz, CDCl3) 7.60 (d, J = 8.0 Hz, 2H, Ar), 7.51-6.98 (m, 31H, Ar), 5.19 (d, J = 2.5 Hz, 2H, CH), 5.03 (d, J = 2.5 Hz, 2H, CH).
[効果等]
上記した触媒の開発により、従来の有機触媒では解決できなかった諸問題の解決、また、これまで合成が難しかった医薬品類の合成開発へと展開できる可能性が高い。また、今回開発した触媒は,これまでに効果的な不斉合成法が無いベンジルニトリルとイミン類の反応において高エナンチオ選択的に生成物を与える。
Claims (2)
- ベンジルニトリルとイミン類の反応において高エナンチオ選択的に生成物を与える触媒として用いられる、下記化学式1で示される光学活性フェニルビスイミダゾリン−遷移金属錯体触媒。
ただし、
M = Pd, Ni, Rh, Ru, Ir, Pt
R = R1CO, R2SO2, alkyl, aryl R1,R2はalkyl基またはaryl基
X = Cl, Br, I, OTf, CF3CO2, CH3CO2, H2O, SbF5, BF4, ClO4である。 - 請求項1に記載の光学活性フェニルビスイミダゾリン−遷移金属錯体触媒を用いて、ベンジルニトリルとイミン類の反応において高エナンチオ選択的に生成物を得る方法。
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JP5866709B2 (ja) * | 2011-12-29 | 2016-02-17 | 国立大学法人 千葉大学 | ビスイミダゾリジンピンサー型錯体、及び、ビスイミダゾリジンピンサー型錯体並びにそれらの製造方法 |
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JP2001106965A (ja) * | 1999-10-06 | 2001-04-17 | Shikoku Chem Corp | ビスイミダゾリン化合物のカルボン酸塩を用いたエポキシ/ポリエステル系粉体塗料 |
JP4413507B2 (ja) * | 2003-02-28 | 2010-02-10 | 独立行政法人科学技術振興機構 | ピンサー型金属錯体及びその製造方法、並びにピンサー型金属錯体触媒 |
JP4747298B2 (ja) * | 2005-10-07 | 2011-08-17 | 国立大学法人 千葉大学 | ビスイミダゾリン配位子及びそれを用いた触媒 |
JP2008069268A (ja) * | 2006-09-14 | 2008-03-27 | Konica Minolta Holdings Inc | 有機エレクトロルミネッセンス素子材料、有機エレクトロルミネッセンス素子、表示装置及び照明装置 |
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