WO2003076410A1 - Procede de cycloaddition asymetrique intramoleculaire [3+2] d'hydrazones - Google Patents
Procede de cycloaddition asymetrique intramoleculaire [3+2] d'hydrazones Download PDFInfo
- Publication number
- WO2003076410A1 WO2003076410A1 PCT/JP2003/002862 JP0302862W WO03076410A1 WO 2003076410 A1 WO2003076410 A1 WO 2003076410A1 JP 0302862 W JP0302862 W JP 0302862W WO 03076410 A1 WO03076410 A1 WO 03076410A1
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- WO
- WIPO (PCT)
- Prior art keywords
- asymmetric
- reaction
- intramolecular
- cycloaddition
- substituent
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
Definitions
- the invention of this application relates to an asymmetric intramolecular [3 + 2] cycloaddition reaction of a hydrazone derivative. More specifically, the invention of this application relates to a method for easily and efficiently asymmetric intramolecular [3 + 2] cyclization of a hydrazone derivative under mild conditions.
- One useful method for constructing a nitrogen-containing five-membered ring skeleton is the [3 + 2] cycloaddition reaction, which has been studied for a long time.
- cycloaddition reactions using highly reactive 1,3-dipoles such as ditrons have been widely studied, and examples of catalytic asymmetric reactions using asymmetric Lewis acids have also been reported.
- the [3 + 2] cycloaddition reaction of aryl and acyl hydrazone in 1970 Hesse reported the first cycloaddition reaction of aryl and acyl hydrazone with alkene using a protonic acid as a catalyst. Furthermore, in 1979, it was reported by Griggs et al.
- Intramolecular [3 + 2] asymmetric cycloaddition can not only efficiently construct polycycles but also induce cyclic 1,3-diamines by cleaving N-N bonds of products. Therefore, its usefulness is high.
- the invention of this application has been made in view of the circumstances as described above, and overcomes the limitations of the prior art, and under ordinary mild conditions, has high stereoselectivity and high yield in the asymmetric intramolecular hydrazone. It is an object of the present invention to provide a method for performing a [3 + 2] cycloaddition reaction. Disclosure of the invention
- ⁇ 1 and ⁇ 2 each represent, identically or differently, a hydrogen atom or a halogen atom, and at least one of ⁇ 1 and ⁇ 2 represents a halogen atom.
- R 1 R 2 , R 3 , R 4 and R 5 each independently or independently represent a hydrogen atom or a hydrocarbon group which may have a substituent or a hetero atom
- R 1 and R 2 , R 3 and R 4 may be linked by a hydrocarbon chain which may have a substituent or a hydrocarbon chain having a different atom to form a ring
- X represents a substituent or It indicates a hydrocarbon chain or a hetero atom that may have a hetero atom.
- the invention of the present application also provides, secondly, the above-described asymmetric intramolecular [3 + 2] cycloaddition reaction method carried out in the presence of a primary alcohol, and thirdly, that the primary alcohol is n-propanol. And a method for asymmetric intramolecular [3 + 2] cycloaddition reaction.
- the invention of this application is directed to any one of the above asymmetric compounds wherein the zirconia alkoxide used in the catalyst system is Zr (0'Bu) 4 or Zr (OPr) 4. It also provides an intramolecular [3 + 2] cycloaddition reaction method.
- the inventors of the present application have found that the use of a catalytic amount of zirconium triflate allows the intermolecular [3 + 2] addition reaction of hydrazone to proceed efficiently even under mild conditions such as at room temperature or in an organic solvent. Further, as a result of continuing intensive studies on the development of catalytic asymmetric reactions, the present invention has been achieved.
- Y 1 and Y 2 are the same or different and each represent a hydrogen atom or a halogen atom, and at least one of ⁇ 1 and ⁇ 2 represents a halogen atom.
- RR 2 , R 3 , R 4 and R 5 are the same or different and are a hydrogen atom or a hydrocarbon group which may have a substituent or a hetero atom. Further, R 1 and R 2 , R 3 and R 4 may be linked by a hydrocarbon chain which may have a substituent or a heteroatom to form a ring.
- X is a hydrocarbon chain or a hetero atom which may have a substituent or a hetero atom.
- the RR 2 , R 3, and R 4 are not particularly limited as long as they do not inhibit intramolecular [3 + 2] cyclization of the hydrazone derivative.
- alkyl groups such as methyl, ethyl, n-propyl, i-propyl, and t-butyl, and aromatic groups such as phenyl and naphthyl, and halogen atoms and substitutions containing 0, N, and S are included.
- a hydrocarbon group having a group is exemplified. Of these, lower alkyl groups such as methyl and ethyl are preferred.
- R 1 and R 2 and R 3 and R 4 each form a ring, for example, One j one CH 2 CH (CH 3 ) CH 2 CH 2 —, CH 2 CH 2 OCH 2 CH 2 —, O CH 2 CH 2 0—, S CH 2 CH 2 S— and the like.
- Examples of X include, for example, —CH 2 —, —CH (CH 3 ) —, —O—, and —S.
- R 5 may be the same as R i to R 4 , but has a hetero atom such as carboxy group, nitro group, sulfonic acid group, etc.
- Preferred examples include a hydrocarbon group and an aromatic group.
- the human Dorazon derivatives those wherein R 5 is a Ashiru group, for example - CO_Me, - CO-E t , - CO- P r, - CO- P h, _CO- P h- N0 compounds such 2 like
- R 5 has a benzoyl group having a 412-nitro group, a benzoyl group having no 412-nitro group, or a benzoyl group having a substituent other than a 4-nitro group are preferable. It is exemplified.
- the hydrazone derivative may be reacted in the presence of the catalyst system as described above, and the reaction conditions are not particularly limited.
- the reaction yield and stereoselectivity are increased, which is preferable.
- the type and amount of the primary alcohol added at this time are not limited.
- n-propanol may be added in an amount of 5 to 10 equivalents to the binaphthol derivative (II).
- the other reaction conditions are not particularly limited. It is characterized by high yield and high stereoselectivity and progress of asymmetric intramolecular [3 + 2] cycloaddition reaction.
- the reaction solvent various organic solvents are exemplified, and preferably, dichloromethane, benzene, fluorobenzene, toluene and the like are exemplified. As described above, the addition of a primary alcohol to the reaction solvent is preferable because the reaction yield and stereoselectivity are further improved.
- the nitrogen-containing compound produced by the method of the present invention may be further reacted and converted by various organic synthesis techniques to obtain a desired substance.
- optically active 1,3-diamin can be induced by cleaving the N—N bond of the cyclized product.
- general operations such as extraction, separation, filtration, washing, and drying are performed. May go.
- the present invention will be described in more detail with reference to examples. ⁇ Obviously, the invention of this application is not limited to the following examples.
- 4-Nitrobenzoylhydrazone is prepared by adding 1 equivalent of aldehyde ((S) -Citronel lal) to a solution of 12-trobenzylhitrazin in dimethylformamide (DMF). 7-trimethyl 6-octenal and 7-methy 6-octenal were determined by the method described in the literature), and the mixture was stirred at room temperature for several hours until the aldehyde disappeared. The reaction was stopped by adding water, and extracted three times with ethyl acetate. The organic layers were combined, washed three times with water and once with a saturated saline solution, and dried over anhydrous sodium sulfate.
- aldehyde ((S) -Citronel lal)
- DMF dimethylformamide
- Example 2 shows the results.
- Table 3 shows the reaction time, reaction yield, and stereoselectivity.
- the trans form was preferentially obtained from the (R) form binaphthol, and the cis form was obtained from the (S) form binaphthol.
- the yield and selectivity were also improved with a substrate having a thioketal group at the i3 position.
- 1,3-diamines could be used not only as chiral ligands but also for the synthesis of analogs of the anticancer drug cisplatin.
- nitrile form was formed in the post-treatment.
- This nitrile form can be derived not only into aminomethylcyclohexylamine by reduction of nitrile group and deprotection of benzoyl group, but also into j8-amino acid. Can be said to be useful compounds.
- the invention of this application provides a method for performing intramolecular [3 + 2] cycloaddition of hydrazone with high stereoselectivity and yield under ordinary mild conditions.
- Such asymmetric intramolecular [3 + 2] cycloaddition is highly useful as a simple method for stereoselectively synthesizing nitrogen-containing compounds often found in natural products and the like.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003574631A JP4215648B2 (ja) | 2002-03-11 | 2003-03-11 | ヒドラゾンの不斉分子内[3+2]環化付加反応方法 |
US10/507,309 US7351831B2 (en) | 2002-03-11 | 2003-03-11 | Process for asymmetric intramolecular [3+2] cyclo-addition of hydrazones |
EP03710300.9A EP1489072B1 (en) | 2002-03-11 | 2003-03-11 | Process for asymmetric intramolecular (3+2) cyclo-addition of hydrazones |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002-66161 | 2002-03-11 | ||
JP2002066161 | 2002-03-11 |
Publications (1)
Publication Number | Publication Date |
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WO2003076410A1 true WO2003076410A1 (fr) | 2003-09-18 |
Family
ID=27800247
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/002862 WO2003076410A1 (fr) | 2002-03-11 | 2003-03-11 | Procede de cycloaddition asymetrique intramoleculaire [3+2] d'hydrazones |
Country Status (4)
Country | Link |
---|---|
US (1) | US7351831B2 (ja) |
EP (1) | EP1489072B1 (ja) |
JP (1) | JP4215648B2 (ja) |
WO (1) | WO2003076410A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7667078B2 (en) * | 2004-03-09 | 2010-02-23 | Japan Science And Technology Agency | Asymmetric reaction catalyst and method for preparing optically active compound using the same |
CN103073393B (zh) * | 2013-01-10 | 2015-04-15 | 北京大学 | 一种羟基取代的稠环芳香化合物的制备方法 |
-
2003
- 2003-03-11 EP EP03710300.9A patent/EP1489072B1/en not_active Expired - Fee Related
- 2003-03-11 US US10/507,309 patent/US7351831B2/en not_active Expired - Fee Related
- 2003-03-11 JP JP2003574631A patent/JP4215648B2/ja not_active Expired - Fee Related
- 2003-03-11 WO PCT/JP2003/002862 patent/WO2003076410A1/ja active Application Filing
Non-Patent Citations (4)
Title |
---|
FOUCHET B. ET AL.: "(3+2) Intramolecular cationic cycloadditions and 1,3-dipolar cycloadditions of phenylhydrazones", TETRAHEDRON LETTERS, vol. 22, no. 14, 1981, pages 1333 - 1336, XP002967662 * |
KABAYASHI SHU ET AL.: "Chiral catalyst optimization using both solid-phase and liquid-phase methods in asymmetric Aza Diels-Alder reactions", ORGANIC LETTERS, vol. 2, no. 9, 2000, pages 1225 - 1227, XP002967663 * |
KOBAYASHI SHU ET AL.: "Asymmetric intramolecular (3 + 2) cycloaddition reactions of acylhydrazones/olefins using a chiral zirconium catalyst", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 124, no. 46, 2002, pages 13678 - 13679, XP002967661 * |
SAKANE SOICHI ET AL.: "Asymmetric cyclization of unsaturated aldehydes catalyzed by a chiral", TETRAHEDRON, vol. 42, no. 8, 1986, pages 2203 - 2209, XP002967664 * |
Also Published As
Publication number | Publication date |
---|---|
US7351831B2 (en) | 2008-04-01 |
EP1489072B1 (en) | 2016-01-20 |
EP1489072A4 (en) | 2005-11-30 |
EP1489072A1 (en) | 2004-12-22 |
JPWO2003076410A1 (ja) | 2005-07-07 |
US20050165237A1 (en) | 2005-07-28 |
JP4215648B2 (ja) | 2009-01-28 |
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