JP2010188267A - 光学活性フェニルビスイミダゾリン−遷移金属錯体触媒 - 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 Download PDFInfo
- Publication number
- JP2010188267A JP2010188267A JP2009034366A JP2009034366A JP2010188267A JP 2010188267 A JP2010188267 A JP 2010188267A JP 2009034366 A JP2009034366 A JP 2009034366A JP 2009034366 A JP2009034366 A JP 2009034366A JP 2010188267 A JP2010188267 A JP 2010188267A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- optically active
- metal complex
- phebim
- imidazoline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
【解決手段】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-遷移金属錯体触媒とする。
【化1】
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。
【選択図】なし
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 (1)
- 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。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009034366A JP5334252B2 (ja) | 2009-02-17 | 2009-02-17 | 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 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009034366A JP5334252B2 (ja) | 2009-02-17 | 2009-02-17 | 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 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2010188267A true JP2010188267A (ja) | 2010-09-02 |
JP5334252B2 JP5334252B2 (ja) | 2013-11-06 |
Family
ID=42814909
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009034366A Expired - Fee Related JP5334252B2 (ja) | 2009-02-17 | 2009-02-17 | 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 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5334252B2 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013139417A (ja) * | 2011-12-29 | 2013-07-18 | Chiba Univ | 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 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
JP2004262832A (ja) * | 2003-02-28 | 2004-09-24 | Japan Science & Technology Agency | 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 |
JP2007099730A (ja) * | 2005-10-07 | 2007-04-19 | Chiba Univ | 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 |
-
2009
- 2009-02-17 JP JP2009034366A patent/JP5334252B2/ja not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
JP2004262832A (ja) * | 2003-02-28 | 2004-09-24 | Japan Science & Technology Agency | 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 |
JP2007099730A (ja) * | 2005-10-07 | 2007-04-19 | Chiba Univ | 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 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013139417A (ja) * | 2011-12-29 | 2013-07-18 | Chiba Univ | 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 |
Also Published As
Publication number | Publication date |
---|---|
JP5334252B2 (ja) | 2013-11-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5284269B2 (ja) | ルテニウムを主成分とした触媒錯体、およびオレフィンメタセシスのための前記錯体の使用 | |
Hartwig et al. | Iridium-catalyzed allylic substitution | |
Zhang et al. | Chiral Brønsted Acid‐Mediated Enantioselective Organocatalytic Three‐Component Reaction for the Construction of Trifluoromethyl‐Containing Molecules | |
Owens et al. | Iridium (III)-bis (oxazolinyl) phenyl catalysts for enantioselective C–H functionalization | |
Wen et al. | Enantioselective organocatalytic phospha-Michael reaction of α, β-unsaturated ketones | |
Wang et al. | Synthesis, structure and catalytic properties of CNN pincer palladium (II) and ruthenium (II) complexes with N-substituted-2-aminomethyl-6-phenylpyridines | |
Demir et al. | The first used half sandwich ruthenium (II) complexes bearing benzimidazole moiety for N-alkylation of amines with alcohols | |
Ran et al. | α-Regioselective [3+ 2] annulations with Morita–Baylis–Hillman carbonates of isatins and 2-nitro-1, 3-enynes | |
Sharma et al. | (η6-Benzene) Ru (II) half-sandwich complexes of pyrazolated chalcogenoethers for catalytic activation of aldehydes to amides transformation | |
Li et al. | Nickel-catalyzed substitution reactions of propargyl halides with organotitanium reagents | |
CN112824422B (zh) | 一种手性二茂铁-吲哚双膦配体及其制备方法和其应用 | |
Yonson et al. | Alkene hydroamination with a chiral zirconium catalyst. Connecting ligand design, precatalyst structure and reactivity trends | |
JP6048762B2 (ja) | 光学活性β−ヒドロキシ−α−アミノカルボン酸エステルの製造方法 | |
Fang et al. | Highly enantioselective copper-catalyzed allylic alkylation with atropos phosphoramidites bearing a D2-symmetric biphenyl backbone | |
JP5334252B2 (ja) | 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 | |
You et al. | Novel bis-N-[2-(diphenylphosphino) ferrocenylcarbonyl] diaminocyclohexane ligands: application in asymmetric allylic alkylation of imino esters with simple allyl carbonate | |
US8729303B2 (en) | 2,2′,6,6′-tetrasubstituted aminophosphine ligand and its synthesis method | |
JP4917064B2 (ja) | スルホニルイミデートのアリル化反応方法 | |
JP6289310B2 (ja) | 触媒又はその前駆体並びにこれらを利用した二酸化炭素の水素化方法及びギ酸塩の製造方法 | |
Chen et al. | Palladium-catalyzed three-component reaction of ferrocenyl allenes, aryl iodides and active methylene compounds: regio-and stereoselective synthesis of (E)-alkenylferrocenes | |
WO2019208023A1 (ja) | 光学活性希土類錯体、この錯体からなる不斉触媒、及び、この不斉触媒を用いた光学活性有機化合物の製造方法 | |
JP4918257B2 (ja) | 不斉還元方法 | |
CN116283672B (zh) | 一种β-烯丙基苯乙胺衍生物的合成方法及应用 | |
JP4307106B2 (ja) | 5−アルキリデン−2−オキサゾリジノン類の製造方法 | |
JP2013142071A (ja) | ピロリジニル−スピロオキシインドール誘導体及びその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20111122 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20121122 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121218 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130207 |
|
A072 | Dismissal of procedure |
Free format text: JAPANESE INTERMEDIATE CODE: A073 Effective date: 20130611 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130723 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130726 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5334252 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |