JP4911528B2 - 光学活性ヒドロキシメチル化化合物の製法及びそのための触媒 - Google Patents
光学活性ヒドロキシメチル化化合物の製法及びそのための触媒 Download PDFInfo
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- JP4911528B2 JP4911528B2 JP2007500589A JP2007500589A JP4911528B2 JP 4911528 B2 JP4911528 B2 JP 4911528B2 JP 2007500589 A JP2007500589 A JP 2007500589A JP 2007500589 A JP2007500589 A JP 2007500589A JP 4911528 B2 JP4911528 B2 JP 4911528B2
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
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- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/487—Saturated compounds containing a keto group being part of a ring containing hydroxy groups
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- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
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- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
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- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
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- C07B2200/07—Optical isomers
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Description
ところで、ホルムアルデヒドは、有機合成において1炭素増炭素反応の最も重要な求電子剤であり、ヒドロキシメチル化反応においてもホルムアルデヒドをルイス酸で活性化する方法がしばしば用いられてきた。しかしながら、有機溶媒中で反応を行うためには、ホルムアルデヒド重合体から熱分解により発生させる必要があり、安全性や利便性の点で問題が大きい。また、ホルムアルデヒドの水溶液であるホルマリンは安価で取り扱いも容易であるが、通常のルイス酸は加水分解を受けやすいため、ホルマリンをルイス酸によって活性化することは困難である。
一方、ビスマス塩は高いルイス酸性を有しており、反応の種類によっては(特に水溶液中の反応)、スカンジウムよりも優れた触媒活性を示すことが知られている。しかも、ビスマスカチオンはほとんど無毒であり、スカンジウムよりも安価である。しかしながら、ビスマス塩を用いる触媒的不斉反応としては、塩化メチレン中でのアルデヒドのトリメチルシリルシアニドによるシアノ化反応が唯一知られているに過ぎない(非特許文献10)。
特に、下式(化2)
溶媒中の配位子とBi(OTf)3等のBiY3の各濃度は0.01〜0.1mol/l程度が好ましい。
R5〜R7は好ましくは以下のとおりである。
R5は水素原子又はアルキル基を表し、R6はアルキル基、アルキルアリール基、アリール基又はスルフィドを表し、但し、R5とR6は共にその一部が芳香族環を形成していてもよい炭素及び任意にヘテロ原子、好ましくは炭素原子から成る5〜6員環を形成してもよく、R7は水素原子、アルキル基、アルキルアリール基、又はアリール基を表す。
又、R5とR7はそれぞれ異なる。
反応温度は−30℃〜常温、より好適には−15〜0℃の範囲である。
反応時間は、適宜定めてもよく、例えば、0.5〜50時間である。
Claims (4)
- 水溶液中又は水と有機溶媒との混合溶媒中で、下式(化2)
- (前記キラルなビピリジン化合物からなる配位子又はその対称体/前記ルイス酸)で表されるモル比を2.5以上とする請求項1に記載の製法。
- さらに2,2'−ビピリジンを添加剤として加える請求項1又は2に記載の製法。
- 下式(化2)
下式(式1)
Priority Applications (1)
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JP2007500589A JP4911528B2 (ja) | 2005-01-31 | 2006-01-27 | 光学活性ヒドロキシメチル化化合物の製法及びそのための触媒 |
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JP2005022643 | 2005-01-31 | ||
JP2005022643 | 2005-01-31 | ||
JP2007500589A JP4911528B2 (ja) | 2005-01-31 | 2006-01-27 | 光学活性ヒドロキシメチル化化合物の製法及びそのための触媒 |
PCT/JP2006/301293 WO2006080425A1 (ja) | 2005-01-31 | 2006-01-27 | 光学活性ヒドロキシメチル化化合物の製法及びそのための触媒 |
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JPWO2006080425A1 JPWO2006080425A1 (ja) | 2008-06-19 |
JP4911528B2 true JP4911528B2 (ja) | 2012-04-04 |
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JP2007500589A Expired - Fee Related JP4911528B2 (ja) | 2005-01-31 | 2006-01-27 | 光学活性ヒドロキシメチル化化合物の製法及びそのための触媒 |
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US (1) | US7541307B2 (ja) |
EP (1) | EP1852412B1 (ja) |
JP (1) | JP4911528B2 (ja) |
DE (1) | DE602006020696D1 (ja) |
WO (1) | WO2006080425A1 (ja) |
Families Citing this family (1)
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EP1724251B1 (en) | 2004-01-30 | 2015-09-16 | Japan Science and Technology Agency | Process for the production of optically active hydroxymethylated compounds |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2001252570A (ja) * | 2000-03-10 | 2001-09-18 | Japan Science & Technology Corp | キラル希土類金属触媒と不斉アルドール反応方法 |
Family Cites Families (1)
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JP3537763B2 (ja) | 2000-12-28 | 2004-06-14 | 独立行政法人 科学技術振興機構 | 水溶液中での不斉アルドール反応用触媒 |
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- 2006-01-27 EP EP06712459A patent/EP1852412B1/en not_active Not-in-force
- 2006-01-27 DE DE602006020696T patent/DE602006020696D1/de active Active
- 2006-01-27 JP JP2007500589A patent/JP4911528B2/ja not_active Expired - Fee Related
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- 2006-01-27 WO PCT/JP2006/301293 patent/WO2006080425A1/ja active Application Filing
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JP2001252570A (ja) * | 2000-03-10 | 2001-09-18 | Japan Science & Technology Corp | キラル希土類金属触媒と不斉アルドール反応方法 |
Also Published As
Publication number | Publication date |
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JPWO2006080425A1 (ja) | 2008-06-19 |
EP1852412A1 (en) | 2007-11-07 |
EP1852412A4 (en) | 2009-03-04 |
US20080139835A1 (en) | 2008-06-12 |
DE602006020696D1 (de) | 2011-04-28 |
US7541307B2 (en) | 2009-06-02 |
WO2006080425A1 (ja) | 2006-08-03 |
EP1852412B1 (en) | 2011-03-16 |
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