JPWO2011062280A1 - 光学活性アルコールの製造方法 - Google Patents
光学活性アルコールの製造方法 Download PDFInfo
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- JPWO2011062280A1 JPWO2011062280A1 JP2011541985A JP2011541985A JPWO2011062280A1 JP WO2011062280 A1 JPWO2011062280 A1 JP WO2011062280A1 JP 2011541985 A JP2011541985 A JP 2011541985A JP 2011541985 A JP2011541985 A JP 2011541985A JP WO2011062280 A1 JPWO2011062280 A1 JP WO2011062280A1
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- 0 CC(C)*(C)(c1cc(C(F)(F)F)cc(C(F)(F)F)c1)O Chemical compound CC(C)*(C)(c1cc(C(F)(F)F)cc(C(F)(F)F)c1)O 0.000 description 7
- VLRWCHKOSBUGMB-UHFFFAOYSA-N CCC(c1cc(C(F)(F)F)cc(C(F)(F)F)c1)=O Chemical compound CCC(c1cc(C(F)(F)F)cc(C(F)(F)F)c1)=O VLRWCHKOSBUGMB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
工程(A)では、ハロゲン化亜鉛、金属アルコキシド、及びRMgY(R;2級の炭化水素基、Y;ハロゲン原子)を反応させて、有機亜鉛化合物ZnR2を得る。
工程(B)では、化合物(1)の存在下、カルボニル化合物と、上記有機亜鉛化合物とを反応させる。
本発明では、工程(A)を行った後、得られた上記有機亜鉛化合物を単離し、次いでこれを反応系に加えることにより、工程(B)を行ってもよい。しかし、本発明では、工程(A)及び工程(B)は完全に分離する必要はない。工程(A)及び工程(B)は連続的に行うことができる。例えば、工程(A)により上記有機亜鉛化合物を得た後、これを単離せずに、続いて化合物(1)及び上記カルボニル化合物を反応系に加え、工程(B)を行うことができる。この方法によれば、工程(A)及び工程(B)を1つの反応槽で行うことができる。
以下の方法により、ジイソプロピル亜鉛(i−Pr2Zn)を用いて、アルデヒドから光学活性第2級アルコールを合成した。
アルデヒド及び有機亜鉛化合物として、表2に示すアルデヒド及び有機亜鉛化合物を用いる他は、上記(1)と同様の方法により、表2に示す光学活性第2級アルコールを合成した。合成スキーム及び結果(収率及びエナンチオマー過剰率)を表2に示す。
ベンズアルデヒドに代えて、3,5−ビス(トリフルオロメチル)アセトフェノンを用い、反応時間及び反応温度を下記記載の時間及び温度とする他は、上記(1)と同様の手順により、光学活性第3級アルコールを得た(「cat」は、上記のホスホロアミド化合物(1a)である。)。合成スキームは以下の通りである。その結果(収率及びエナンチオマー過剰率)を以下に示す。
Claims (9)
- (A)ハロゲン化亜鉛、金属アルコキシド、及びRMgY(R;2級の炭化水素基、Y;ハロゲン原子)を反応させて、有機亜鉛化合物ZnR2を得る工程と、
(B)式(1)で表されるホスホロアミド化合物の存在下、カルボニル化合物と、上記有機亜鉛化合物とを反応させる工程と、を備え、
上記工程(A)において、上記RMgYの量は、上記ハロゲン化亜鉛1当量に対して1.8当量以下である光学活性アルコールの製造方法。
- 上記カルボニル化合物は、アルデヒド化合物である請求項1記載の光学活性アルコールの製造方法。
- Rは2級のアルキル基又はシクロアルキル基である請求項1又は2記載の光学活性アルコールの製造方法。
- 工程(B)において、上記有機亜鉛化合物の量は、上記カルボニル化合物に対して1〜5当量である請求項1乃至3のいずれかに記載の光学活性アルコールの製造方法。
- 工程(A)及び工程(B)は連続的に行う請求項1乃至4のいずれかに記載の光学活性アルコールの製造方法。
- 工程(A)において、上記RMgYの量は、上記ハロゲン化亜鉛1当量に対して1.0〜1.8当量である請求項1乃至5のいずれかに記載の光学活性アルコールの製造方法。
- R2及びR3はフェニル基又はナフチル基である請求項1乃至6のいずれかに記載の光学活性アルコールの製造方法。
- 工程(B)は無溶媒下又は溶媒存在下で行う請求項1乃至7のいずれかに記載の光学活性アルコールの製造方法。
- 工程(B)はアミン化合物の非存在下又は存在下で行う請求項1乃至8のいずれかに記載の光学活性アルコールの製造方法。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011541985A JP5750667B2 (ja) | 2009-11-20 | 2010-11-19 | 光学活性アルコールの製造方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009265527 | 2009-11-20 | ||
JP2009265527 | 2009-11-20 | ||
PCT/JP2010/070745 WO2011062280A1 (ja) | 2009-11-20 | 2010-11-19 | 光学活性アルコールの製造方法 |
JP2011541985A JP5750667B2 (ja) | 2009-11-20 | 2010-11-19 | 光学活性アルコールの製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2011062280A1 true JPWO2011062280A1 (ja) | 2013-04-11 |
JP5750667B2 JP5750667B2 (ja) | 2015-07-22 |
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Application Number | Title | Priority Date | Filing Date |
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JP2011541985A Expired - Fee Related JP5750667B2 (ja) | 2009-11-20 | 2010-11-19 | 光学活性アルコールの製造方法 |
Country Status (2)
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JP (1) | JP5750667B2 (ja) |
WO (1) | WO2011062280A1 (ja) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008111371A1 (ja) * | 2007-03-09 | 2008-09-18 | National University Corporation Nagoya University | ホスホロアミド化合物及びその製造方法、配位子、錯体、触媒、及び光学活性アルコールの製造方法 |
-
2010
- 2010-11-19 JP JP2011541985A patent/JP5750667B2/ja not_active Expired - Fee Related
- 2010-11-19 WO PCT/JP2010/070745 patent/WO2011062280A1/ja active Application Filing
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Publication number | Publication date |
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JP5750667B2 (ja) | 2015-07-22 |
WO2011062280A1 (ja) | 2011-05-26 |
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