JP4613276B2 - 光学活性ピロリジン誘導体 - Google Patents
光学活性ピロリジン誘導体 Download PDFInfo
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- JP4613276B2 JP4613276B2 JP2003404495A JP2003404495A JP4613276B2 JP 4613276 B2 JP4613276 B2 JP 4613276B2 JP 2003404495 A JP2003404495 A JP 2003404495A JP 2003404495 A JP2003404495 A JP 2003404495A JP 4613276 B2 JP4613276 B2 JP 4613276B2
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- pyrrolidine
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- FKCMADOPPWWGNZ-YUMQZZPRSA-N [(2r)-1-[(2s)-2-amino-3-methylbutanoyl]pyrrolidin-2-yl]boronic acid Chemical compound CC(C)[C@H](N)C(=O)N1CCC[C@H]1B(O)O FKCMADOPPWWGNZ-YUMQZZPRSA-N 0.000 title claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 29
- 238000006957 Michael reaction Methods 0.000 claims description 16
- 238000010485 C−C bond formation reaction Methods 0.000 claims description 15
- 238000005882 aldol condensation reaction Methods 0.000 claims description 13
- GWGBNENHEGYJSN-UHFFFAOYSA-N 2,4-dinitrobenzenesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O GWGBNENHEGYJSN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 150000003235 pyrrolidines Chemical class 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 41
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 230000003287 optical effect Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- HAPUOOBIEAPWAZ-JTQLQIEISA-N 2-[[(2s)-pyrrolidin-2-yl]methyl]pyridine Chemical compound C=1C=CC=NC=1C[C@@H]1CCCN1 HAPUOOBIEAPWAZ-JTQLQIEISA-N 0.000 description 9
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- UTQRWQYEEUMJOA-NSHDSACASA-N 2-[2-[(2s)-pyrrolidin-2-yl]ethyl]pyridine Chemical group C([C@H]1NCCC1)CC1=CC=CC=N1 UTQRWQYEEUMJOA-NSHDSACASA-N 0.000 description 5
- GFYJSFUVPAUKJA-JTQLQIEISA-N 3-[[(2s)-pyrrolidin-2-yl]methyl]pyridine Chemical compound C=1C=CN=CC=1C[C@@H]1CCCN1 GFYJSFUVPAUKJA-JTQLQIEISA-N 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 5
- 238000004296 chiral HPLC Methods 0.000 description 5
- 239000011982 enantioselective catalyst Substances 0.000 description 5
- -1 ketone compound Chemical class 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- JKQUXSHVQGBODD-UHFFFAOYSA-N 1-methoxy-4-(2-nitroethenyl)benzene Chemical compound COC1=CC=C(C=C[N+]([O-])=O)C=C1 JKQUXSHVQGBODD-UHFFFAOYSA-N 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- PIAOLBVUVDXHHL-VOTSOKGWSA-N β-nitrostyrene Chemical compound [O-][N+](=O)\C=C\C1=CC=CC=C1 PIAOLBVUVDXHHL-VOTSOKGWSA-N 0.000 description 4
- UTQRWQYEEUMJOA-UHFFFAOYSA-N 2-(2-pyrrolidin-2-ylethyl)pyridine Chemical compound C1CCNC1CCC1=CC=CC=N1 UTQRWQYEEUMJOA-UHFFFAOYSA-N 0.000 description 3
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 3
- 229930182821 L-proline Natural products 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 229960002429 proline Drugs 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HAPUOOBIEAPWAZ-UHFFFAOYSA-N 2-(pyrrolidin-2-ylmethyl)pyridine Chemical compound C=1C=CC=NC=1CC1CCCN1 HAPUOOBIEAPWAZ-UHFFFAOYSA-N 0.000 description 2
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 2
- GFYJSFUVPAUKJA-UHFFFAOYSA-N 3-(pyrrolidin-2-ylmethyl)pyridine Chemical compound C=1C=CN=CC=1CC1CCCN1 GFYJSFUVPAUKJA-UHFFFAOYSA-N 0.000 description 2
- 235000019502 Orange oil Nutrition 0.000 description 2
- HVVNJUAVDAZWCB-YFKPBYRVSA-N [(2s)-pyrrolidin-2-yl]methanol Chemical compound OC[C@@H]1CCCN1 HVVNJUAVDAZWCB-YFKPBYRVSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- JDOZOOBCADNBIJ-UHFFFAOYSA-N lithium;2h-pyridin-2-ide Chemical compound [Li+].C1=CC=N[C-]=C1 JDOZOOBCADNBIJ-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000010502 orange oil Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012746 preparative thin layer chromatography Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- MYKUKUCHPMASKF-VIFPVBQESA-N (S)-nornicotine Chemical compound C1CCN[C@@H]1C1=CC=CN=C1 MYKUKUCHPMASKF-VIFPVBQESA-N 0.000 description 1
- 0 *Cc1ncccc1 Chemical compound *Cc1ncccc1 0.000 description 1
- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYKUKUCHPMASKF-UHFFFAOYSA-N Nornicotine Natural products C1CCNC1C1=CC=CN=C1 MYKUKUCHPMASKF-UHFFFAOYSA-N 0.000 description 1
- WFFHPXGNIIMFHE-YFKPBYRVSA-N O=S1(OC[C@H]2N1CCC2)=O Chemical compound O=S1(OC[C@H]2N1CCC2)=O WFFHPXGNIIMFHE-YFKPBYRVSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
- Catalysts (AREA)
Description
C. F. Barbas IIIら, J. Am. Chem. Soc., 123, 5260 (2001) B. Listら, J. Am. Chem. Soc., 122, 2395 (2000) D. Enders, A. Seki, Synlett, 2002, No.1, 26. S. Saito, M, Nakadai および H. Yamamoto, Synlett, 2001, No.8, 1245 T. Bui and C. F. Barbas III, Tetrahedron Lett., 41, 6951 (2000) J. M. Betancort, K, Sakthivel, R. Thayumanavan および C. F. Barbas III, Tetrahedron Lett., 42, 4441 (2001) A. Alexakis および O. Andrey, Org. Lett., 4, 3611 (2002) T. J. Dickerson および K. D. Janda, J. Am. Chem. Soc., 124, 3220 (2002) G. F. Cooper, K. E. McCarthy, および M. G. Martin, Tetrahedron Lett., 33, 5895 (1992) D. Alker, K. J. Doyle, L. M. Harwood および A. McCregor, Tetrahedron: Asymmetry, 1, 877 (1990)
からなり、マイケル反応とアルドール縮合との何れかでsyn体又はanti体を形成する炭素−炭素結合形成反応の触媒である。
前記光学活性ピロリジン誘導体が、下記式(II)〜(IV)の何れかで示されるものであることが好ましい。
本発明のsyn体又はanti体を形成する炭素−炭素結合形成方法は、前記のsyn体又はanti体を形成する炭素−炭素結合形成反応の触媒の存在下、マイケル反応とアルドール縮合との何れかの反応をして、そこにsyn体又はanti体を形成する炭素−炭素結合形成方法である。
syn体又はanti体を形成する炭素−炭素結合形成方法は、前記のsyn体又はanti体を形成する炭素−炭素結合形成反応の触媒に、2,4−ジニトロベンゼンスルホン酸を加えて、前記反応をするものであってもよい。
(S)−2−(2−ピリジルメチル)−ピロリジンの合成
(S)−2−(3−ピリジルメチル)−ピロリジンの合成
2−ブロモピリジンの代わりに3−ブロモピリジンを用いたこと以外は実施例1と同様である。以下に示す(S)−2−(3−ピリジルメチル)−ピロリジンを橙色油状物として得た(収率62%)。
Rf 0.29 (CHCl3 / iPrNH2 = 19 / 1); [α]D 25 +6.7 (c 0.60, CHCl3); FTIR (neat) ν 3293, 1575, 1478, 1422, 1107, 1027, 715 cm-1; 1H NMR (400 MHz, CDCl3) δ 1.39 (1H, m), 1.67-1.90 (4H, m), 2.74 (1H,d, J = 7.1 Hz), 2.85 (1H,ddd, J = 10.2, 8.3, 6.6 Hz), 3.04 (1H,ddd, J = 10.2, 7.6, 5.1 Hz), 3.24 (1H, quintet, J = 7.1 Hz), 7.22 (1H,ddd, J = 7.8, 4.9, 0.7 Hz), 7.55 (1H,ddd, J = 7.8, 2.1, 1.7 Hz), 8.46 (1H,dd, J = 4.9, 1.7 Hz), 8.48 (1H,d, J = 2.1 Hz); 13C NMR (100 MHz, CDCl3) δ 24.9, 31.3, 39.7, 46.3, 60.1, 123.3, 135.5, 136.4, 147.6, 150.3
(S)−2−(2−ピリジルエチル)−ピロリジンの合成
シクロヘキサノンとβ−ニトロスチレンとの不斉マイケル反応
実施例1と同様の触媒を使用し、表1に示す条件により実施例1に準じて反応を行なった。実施例5においては、溶媒としてクロロホルムの代わりにトルエンを用いた。
触媒として、実施例2で得られた(S)−2−(3−ピリジルメチル)−ピロリジンを光学活性ピロリジン誘導体として用い、実施例1に準じて反応を行なった。
触媒として、実施例3で得られた(S)−2−(2−ピリジルエチル)−ピロリジンを光学活性ピロリジン誘導体として用い、実施例1に準じて反応を行なった。
触媒としてピロリジンを用い、実施例1に準じて反応を行なった。
本実施例では、触媒として、実施例1で得られた光学活性ピロリジン誘導体である(S)−2−(2−ピリジルメチル)−ピロリジンを用いた。
p−メトキシ−β−ニトロスチレンの代わりに、表2Aまたは表2Bに示すニトロ化合物を、実施例12におけるのと同様のモル比で用いたこと以外は、実施例12と同様に反応を行った。得られた生成物について、実施例12と同様に評価を行った。但し、生成物の光学純度(ee)の測定は、分析用キラルHPLC(Chiralpak ASカラム)を用いて行なった。
シクロヘキサノンの代わりに表2Bに示すケトン化合物またはアルデヒド化合物を、そして、p−メトキシ−β−ニトロスチレンの代わりに、β−ニトロスチレンを、実施例12におけるのと同様のモル比で用いたこと以外は、実施例12と同様に反応を行った。得られた生成物について、実施例12と同様に評価を行った。但し、生成物の光学純度(ee)の測定は、実施例17においては、分析用キラルHPLC(Chiralpak ASカラム)を用いて行ない、実施例18においては、分析用キラルHPLC(Chiralpak ADカラム)を用いて行なった。
Claims (4)
- 請求項1に記載のsyn体又はanti体を形成する炭素−炭素結合形成反応の触媒の存在下、マイケル反応とアルドール縮合との何れかの反応をして、そこにsyn体又はanti体を形成する炭素−炭素結合形成方法。
- 前記触媒に、2,4−ジニトロベンゼンスルホン酸を加えて、前記反応をすることを特徴とする請求項3に記載のsyn体又はanti体を形成する炭素−炭素結合形成方法。
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JP5193664B2 (ja) * | 2008-04-21 | 2013-05-08 | 雄二郎 林 | 不斉触媒マイケル反応生成物の製造方法及び医薬化合物の製造方法。 |
JP5392614B2 (ja) * | 2009-10-19 | 2014-01-22 | 国立大学法人高知大学 | 不斉反応触媒及びそれを用いた不斉合成方法 |
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