JP6246202B2 - 3座アミノジカルベン配位子を有する金属錯体及びそれを用いた水素化還元方法 - Google Patents
3座アミノジカルベン配位子を有する金属錯体及びそれを用いた水素化還元方法 Download PDFInfo
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- JP6246202B2 JP6246202B2 JP2015522973A JP2015522973A JP6246202B2 JP 6246202 B2 JP6246202 B2 JP 6246202B2 JP 2015522973 A JP2015522973 A JP 2015522973A JP 2015522973 A JP2015522973 A JP 2015522973A JP 6246202 B2 JP6246202 B2 JP 6246202B2
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- 150000004696 coordination complex Chemical class 0.000 title claims description 87
- 239000003446 ligand Substances 0.000 title claims description 63
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- 238000000034 method Methods 0.000 title claims description 37
- -1 osmium ion Chemical class 0.000 claims description 189
- 125000001424 substituent group Chemical group 0.000 claims description 108
- 125000000623 heterocyclic group Chemical group 0.000 claims description 79
- 125000003118 aryl group Chemical group 0.000 claims description 72
- 125000000217 alkyl group Chemical group 0.000 claims description 70
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 125000003277 amino group Chemical group 0.000 claims description 52
- 125000003545 alkoxy group Chemical group 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 44
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- 125000004423 acyloxy group Chemical group 0.000 claims description 38
- 125000005843 halogen group Chemical group 0.000 claims description 38
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- 238000005984 hydrogenation reaction Methods 0.000 claims description 34
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 31
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 28
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 22
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- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 10
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- 125000003710 aryl alkyl group Chemical group 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
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- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 5
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- ZVENKBGRIGHMRG-UHFFFAOYSA-M carbon monoxide chloro(hydrido)ruthenium triphenylphosphane Chemical compound [C-]#[O+].[H][Ru]Cl.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 ZVENKBGRIGHMRG-UHFFFAOYSA-M 0.000 description 5
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical group CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 125000006634 pentyloxycarbonylamino group Chemical group 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005542 phthalazyl group Chemical group 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- JSSXHAMIXJGYCS-UHFFFAOYSA-N piperazin-4-ium-2-carboxylate Chemical compound OC(=O)C1CNCCN1 JSSXHAMIXJGYCS-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000006410 propenylene group Chemical group 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical group CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000005412 pyrazyl group Chemical group 0.000 description 1
- 125000005495 pyridazyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical class OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006633 tert-butoxycarbonylamino group Chemical group 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 150000003952 β-lactams Chemical class 0.000 description 1
- 150000003953 γ-lactams Chemical class 0.000 description 1
- 150000003954 δ-lactams Chemical class 0.000 description 1
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Description
を有する金属錯体であって、
前記3座アミノジカルベン配位子は、1つの2級アミン基と、
該アミン基を挟んで、下記一般式L1及び/又はL2:
で表される2つの複素環カルベン基と
を有する、金属錯体。
で表される配位子である、前記(1)又は(2)に記載の金属錯体。
[M(A)Y1Y2Z1] ・・・(2)
[M(A)Y1Z1Z2]Y2 ・・・(3)
[式中、Mはルテニウムイオン又はオスミニウムイオン;Aは前記3座アミノジカルベン
配位子;Y1及びY2は同一又は異なって、それぞれ1価のアニオン性配位子;Z1及び
Z2は同一又は異なって、それぞれ単座配位子である。]
で表される組成を有する、前記(1)〜(6)のいずれかに記載の金属錯体。
アミノジカルベン前駆体(I)に金属化合物(II)を反応させ、次いで、化合物(III)を反応させる工程
を備え、
前記アミノジカルベン前駆体(I)は、
1つの2級アミン基と、
該アミン基を挟んで、下記一般式L1’又はL2’:
で表される2つの複素環基と
を有し、
前記金属化合物(II)は、コバルトイオン、ニッケルイオン、銅イオン、ロジウムイオン、パラジウムイオン又は銀イオンを有し、
前記化合物(III)は、下記一般式(4):
MY1Y2Zn ・・・(4)
[式中、Mはルテニウムイオン又はオスミニウムイオン;Y1及びY2は同一又は異なって、それぞれ1価のアニオン性配位子;Zは同一又は異なって、それぞれ単座配位子;nは2〜4の整数を表す。]
で表される、金属錯体の製造方法。
カルボニル化合物又はイミン類の水素化還元方法。
水素化還元されたカルボニル化合物又はイミン類の製造方法。
本発明の金属錯体は、3座アミノジカルベン配位子と、ルテニウムイオン又はオスミニウムイオンとを有する。
で表される2つの複素環カルベン基とを有する。
で表される配位子が挙げられる。
で示される配位子が好ましく、下記一般式(1B)又は(1C):
で示される配位子がより好ましい。Q1a及びQ2aは、同一であるものが好ましく、中でも、メチレン基、エチレン基、プロピレン基及びシクロヘキシレン基から選ばれるいずれかが好ましく、エチレン基が特に好ましい。R3A及びR3Bは、同一であるものが好ましく、中でも、炭素数1〜6の直鎖状アルキル基が特に好ましい。
[M(A)Y1Y2Z1] ・・・(2)
[M(A)Y1Z1Z2]Y2 ・・・(3)
[式中、Mはルテニウムイオン又はオスミニウムイオン;Aは前記3座アミノジカルベン配位子;Y1及びY2は同一又は異なって、それぞれ1価のアニオン性配位子;Z1及びZ2は同一又は異なって、それぞれ単座配位子である。]
で示される組成を有することが好ましい。
で示される金属錯体が好ましく、下記一般式(3B)又は(3C):
で示される金属錯体がより好ましい。Q1a及びQ2aは、同一であるものが好ましく、中でも、メチレン基、エチレン基、プロピレン基及びシクロヘキシレン基から選ばれるいずれかが好ましい。R3A及びR3Bは、同一であるものが好ましく、中でも、炭素数1〜6の直鎖状アルキル基が特に好ましい。
で表される金属錯体が挙げられる。
本発明における金属錯体の製造方法は、特に制限されないが、
方法(A):
特定のアミノジカルベン前駆体(I)に特定の金属化合物(II)を反応させ、次いで、特定の化合物(III)を反応させる工程
を備える方法により得られる。
で表される2つの複素環基とを含有する。
で示されるアミノジカルベン前駆体が好ましく、下記一般式(IB)又は(IC):
で示されるアミノジカルベン前駆体がより好ましい。Q1a及びQ2aは、同一であるものが好ましく、中でも、メチレン基、エチレン基、プロピレン基及びシクロヘキシレン基から選ばれるいずれかが好ましい。R3A及びR3Bは、同一であるものが好ましく、中でも、炭素数1〜6の直鎖状アルキル基が特に好ましい。
MY1Y2Zn ・・・(4)
[式中、Mはルテニウムイオン又はオスミニウムイオン;Y1及びY2は同一又は異なって、それぞれ1価のアニオン性配位子;Zは同一又は異なって、それぞれ単座配位子;nは2〜4の整数を表す。]
で表される化合物である。
で示される金属錯体が好ましく、下記一般式(5C)〜(5F):
で示される金属錯体がより好ましい。Q1a及びQ2aは、同一であるものが好ましく、中でも、メチレン基、エチレン基、プロピレン基及びシクロヘキシレン基から選ばれるいずれかが好ましい。R3A及びR3Bは、同一であるものが好ましく、中でも、炭素数1〜6の直鎖状アルキル基が特に好ましい。
方法(B):
前記アミノジカルベン前駆体(I)に塩基(カリウム−tert−ブトキシド、リチウムヘキサメチレンジシラザン、水素化ナトリウム等)を反応させ、次いで化合物(III)を反応させる工程
を備える方法によっても得られる。
で示される化合物の少なくとも1種を反応させることで容易に調整することができる。また、アミノジカルベン前駆体(I)は、上記方法に限定されず、公知の反応を参考に様々な方法で合成することができる。
次に、本発明の金属錯体の存在下、水素供与体を用いてカルボニル化合物又はイミン類を還元する水素化還元方法について説明する。
<分析方法>
装置:「島津GC−17A」(株式会社島津ジーエルシー製)
注入口温度:280℃
検出温度:280℃
カラム:「DB−1MS(60m)」(J&W Scientific社製)
カラム温度:40℃(5分)−15℃/分−320℃
検出器:水素炎イオン化検出器(FID)
を使用した。
L GX−500」を使用した。
次の反応式によりルテニウム錯体1を製造した。
窒素雰囲気下、ジエタノ―ルアミン12g(114mmol)、トリエチルアミン62mL(Et3N、445mmol)及びトルエン(160mL)を500mL3つ口フラスコに加え、塩化パラトルエンスルホニル72g(TsCl、378mmol)を添加した。添加終了後、25℃で1時間攪拌したのち、固体分をろ別した。ろ液に蒸留水100mLを加えて分液後、有機層を飽和食塩水(50mL×2)で洗浄した。有機層を硫酸ナトリウムで乾燥し、減圧下で濃縮することにより、粗生成物を得た。この粗生成物をシリカゲルカラムクロマトグラフィー(展開液 トルエン:アセトン=50:1(v/v))で精製することにより、化合物7を52g(91mmol、収率80%)得た。
1H−NMR(500MHz、CDCl3):δ=7.76(d,J=7.9Hz,4H)、7.61(d,J=7.9Hz,2H)、7.36(d,J=7.9Hz,4H)、7.29(d,J=7.9Hz,2H)、4.11(t,J=5.8Hz,4H)、3.38(t,J=5.8Hz,4H)、2.46(s,6H)、2.43(s,3H)。
前記で製造した化合物7を15g(26.4mmol)、窒素雰囲気下の300mL3つ口フラスコに加え、さらに4−メチル−2−ペンタノン(150mL)及び1−ブチルイミダゾール7.0mL(53.6mmol)を加え、3時間加熱還流を行った。放冷後、オイル状沈降物を4−メチル−2−ペンタノン(50mL×2)で洗浄し、減圧下で濃縮することにより化合物8を19.8g(24.3mmol、収率92%)得た。
1H−NMR(500MHz、重DMSO):δ=9.24(s,2H)、7.79(s,2H)、7.77(s,2H)、7.63(d,J=7.9Hz,2H)、7.49(d,J=7.9Hz,4H)、7.40(d,J=7.9Hz,2H)、7.12(d,J=7.9Hz,4H)、4.41(t,J=6.4Hz,4H)、4.15(t,J=7.3Hz,4H)、3.65(t,J=6.4Hz,4H)、2.41(s,3H)、2.29(s,6H)、1.75(q,J=7.3Hz,4H)、1.26(quin,J=7.3Hz,4H)、0.89(d,J=7.3Hz,6H)。
前記で製造した化合物8を7.2g(8.82mmol)、窒素雰囲気下の100mL3つ口フラスコに加え、さらに濃臭化水素酸(30mL)を加え、14時間加熱還流を行った。放冷後、溶液のpHが7以上になるまで飽和炭酸水素ナトリウム水を加え、固形部をろ別した後、ろ液部を減圧下で濃縮した。濃縮残渣に2−プロパノ―ル(300mL)を加え、固体分をろ別し、ろ液部を減圧下で濃縮した。得られたオイル状化合物に水(5mL)を加え、その溶液を強塩基I型陰イオン交換樹脂(Cl形、ダウエックス(TM) 1×4 200−400メッシュ、30mL)を充填したカラムに通液することにより化合物9を3.4g(8.71mmol、収率99%)得た。
1H−NMR(500MHz、重DMSO):δ=9.46(s,2H)、7.80(s,4H)、4.23(t,J=5.8Hz,4H)、4.19(t,J=7.3Hz,4H)、2.93(m,4H)、1.78(q,J=7.3Hz,4H)、1.26(quin,J=7.3Hz,4H)、0.91(d,J=7.3Hz,6H)。
前記で製造した化合物9を3.4g(8.71mmol)、窒素雰囲気下の200mLの3つ口フラスコに加え、さらにメタノール(80mL)を加え、−25℃に冷却した。さらに酸化銀2.1g(9.06mmol)を加え、−25℃で6時間攪拌した。溶液を−25℃に保ったまま濾過を行って固体分をろ別し、ろ液部を減圧下で濃縮することで化合物10を3.74g(8.12mmol、収率93%)得た。
1H−NMR(500MHz、重DMSO):δ=7.49(m,4H)、4.18(m,4H)、4.11(m,4H)、2.95(m,4H)、1.76(m,4H)、1.27(m,4H)、0.89(m,6H)。
前記で製造した化合物10を3.74g(8.12mmol)、窒素雰囲気下の500mL3つ口フラスコに加え、さらにアセトニトリル(190mL)を加え、50℃に加熱した。さらにカルボニルクロロヒドリドトリス(トリフェニルホスフィン)ルテニウム(II)7.48g(8.08mmol)を加え、50℃で3時間攪拌した。放冷後、固体分をろ別し、ろ液部を減圧下で濃縮した。濃縮残渣にジクロロメタン(30mL)を加えて、溶液をヘキサン(300mL)に注ぎ、生じる固体部をろ取した。この固体をジクロロメタン/ヘキサンで再結晶することにより目的のルテニウム錯体1を2.3g(3.08mmol、収率38%)得た。ここでは、前記工程においてろ液を濃縮してから行ったが、濃縮せずにそのまま用いた場合も、同様にルテニウム錯体1が得られた。
1H−NMR(500MHz、重CD2Cl2):δ=7.5−7.2(m,17H)、6.98(s,1H)、6.93(s,1H)、4.54(t,J=5.8Hz,1H)、4.23(d,J=5.8Hz,1H)、4.15(d,J=5.8Hz,1H)、3.88(m,1H)、3.8−3.7(m,2H)、3.10(br,1H,N−H)、3.1−2.9(m,4H)、2,72(d,J=5.8Hz,1H)、2.19(m,3H)、1.65(m,1H)、1.48(m,1H)、1.31(m,1H)、1.3−1.1(m,3H)、1.05(m,2H)、0.80(t,J=5.8Hz,1H)、−7.61(d,2JPH=23.5Hz,1H)
13C―NMR(150MHz、CD2Cl2):δ=207(d,Ru−CO)。
晶系:三斜晶系
空間群:P−1
格子定数:a=9.338(5)、b=12.141(6)、c=19.562(11)(単位はÅ(オングストローム))、β=78.89(3)、V=2087(2)(Å3(立方オングストローム))。
次の反応式によりルテニウム錯体2を製造した。
前記実施例1−1で製造した化合物7を15g(26.4mmol)、窒素雰囲気下の300mL3つ口フラスコに加え、さらに4−メチル−2−ペンタノン(150mL)及び1−メチルイミダゾール4.2mL(53.2mmol)を加え、3時間加熱還流を行った。放冷後、オイル状沈降物を4−メチル−2−ペンタノン(50mL×2)で洗浄し、減圧下で濃縮することにより化合物12を18.2g(24.9mmol、収率94%)得た。
1H−NMR(500MHz、重DMSO):δ=9.12(s,2H)、7.73(s,2H)、7.65(s,2H)、7.61(d,J=7.9Hz,2H)、7.47(d,J=7.9Hz,4H)、7.37(d,J=7.9Hz,2H)、7.10(d,J=7.9Hz,4H)、4.38(t,J=6.2Hz,4H)、3.82(s,6H)、3.63(t,J=7.3Hz,4H)、2.39(s,3H)、2.27(s,6H)。
前記で製造した化合物11を8.0g(10.9mmol)、窒素雰囲気下の100mL3つ口フラスコに加え、さらに濃臭化水素酸(30mL)を加え、14時間加熱還流を行った。放冷後、溶液のpHが7以上になるまで飽和炭酸水素ナトリウム水を加え、固形部をろ別した後、ろ液部を減圧下で濃縮した。濃縮残渣に2−プロパノ―ル(300mL)を加え、固体分をろ別し、ろ液部を減圧下で濃縮した。得られたオイル状化合物に水(5mL)を加え、その溶液を強塩基I型陰イオン交換樹脂(Cl形、ダウエックス(TM) 1×4 200−400メッシュ、30mL)を充填したカラムに通液することにより化合物12を3.2g(10.45mmol、収率96%)得た。
1H−NMR(500MHz、重DMSO):δ=9.14(s,2H)、7.72(s,2H)、7.70(s,2H)、4.22(t,J=5.9Hz,4H)、3.87(s,6H)、2.91(m,4H)。
前記で製造した化合物12を3.2g(10.45mmol)、窒素雰囲気下の200mLの3つ口フラスコに加え、さらにメタノール(80mL)を加え、−25℃に冷却した。さらに酸化銀2.5g(10.79mmol)を加え、−25℃で6時間攪拌した。溶液を−25℃に保ったまま濾過を行って固体分をろ別し、ろ液部を減圧下で濃縮することで化合物13を3.2g(8.49mmol、収率81%)得た。
1H−NMR(500MHz、重DMSO):δ=7.46(s,2H)、7.43(s,2H)、4.19(m,4H)、3.77(s,6H)、2.93(m,4H)。
前記で製造した化合物13を3.06g(8.12mmol)、窒素雰囲気下の500mL3つ口フラスコに加え、さらにアセトニトリル(190mL)を加え、50℃に加熱した。さらにカルボニルクロロヒドリドトリス(トリフェニルホスフィン)ルテニウム(II)7.48g(8.08mmol)を加え、50℃で3時間攪拌した。放冷後、固体分をろ別し、ろ液部を減圧下で濃縮した。濃縮残渣にジクロロメタン(30mL)を加えて、溶液をヘキサン(300mL)に注ぎ、生じる固体部をろ取した。この固体をジクロロメタン/ヘキサンで再結晶することにより目的のルテニウム錯体2を1.9g(2.87mmol、収率35%)得た。ここでは、前記工程においてろ液を濃縮してから行ったが、濃縮せずにそのまま用いた場合も、同様にルテニウム錯体2が得られた。
1H−NMR(500MHz、CD2Cl2):δ=7.5−7.2(m,17H)、6.96(s,1H)、6.92(s,1H)、4.54(t,J=5.8Hz,1H)、4.23(d,J=5.8Hz,1H)、4.15(d,J=5.8Hz,1H)、3.82(s,6H)、3.10(br,1H,N−H)、3.1−2.9(m,4H)、2,72(d,J=5.8Hz,1H)、2.19(m,3H)、−7.58(d,2JPH=23.1Hz,1H)
13C―NMR(150MHz、重DMSO):δ=204(d,Ru−CO)。
次の反応式によりルテニウム錯体3を製造した。
前記実施例1−1で製造した化合物7を15g(26.4mmol)、窒素雰囲気下の300mL3つ口フラスコに加え、さらに4−メチル−2−ペンタノン(150mL)及び1−メチルベンゾイミダゾール7.1g(53.7mmol)を加え、3時間加熱還流を行った。放冷後、オイル状沈降物を4−メチル−2−ペンタノン(50mL×2)で洗浄し、減圧下で濃縮することにより化合物14を18.1g(21.8mmol、収率82%)得た。
1H−NMR(500MHz、重DMSO):δ=9.74(s,2H)、8.04(m,2H)、7.98(m,2H)、7.69(m,4H)、7.48(d,J=8.5Hz,4H)、7.32(d,J=8.5Hz,2H)、7.09(d,J=8.5Hz,4H)、7.07(d,J=8.5Hz,H)、4.78(t,J=6.0Hz,4H)、4.06(s,6H)、3.89(t,J=6.0Hz,4H)、2.27(s,9H)。
前記で製造した化合物14を9.1g(10.9mmol)、窒素雰囲気下の100mL3つ口フラスコに加え、さらに濃臭化水素酸(30mL)を加え、14時間加熱還流を行った。放冷後、溶液のpHが7以上になるまで飽和炭酸水素ナトリウム水を加え、固形部をろ別した後、ろ液部を減圧下で濃縮した。濃縮残渣に2−プロパノ―ル(300mL)を加え、固体分をろ別し、ろ液部を減圧下で濃縮した。得られたオイル状化合物に水(5mL)を加え、その溶液を強塩基I型陰イオン交換樹脂(Cl形、ダウエックス(TM) 1×4 200−400メッシュ、30mL)を充填したカラムに通液することにより化合物15を3.6g(8.86mmol、収率81%)得た。
1H−NMR(500MHz、重DMSO):δ=10.06(s,2H)、8.08(d,J=7.5Hz,2H)、7.97(d,J=7.5Hz,2H)、7.67(t,J=7.5Hz,2H)、7.63(t,J=7.5Hz,2H)、4.66(m,4H)、4.08(s,6H)、3.17(m,4H)。
前記で製造した化合物15を3.6g(8.86mmol)、窒素雰囲気下の200mLの3つ口フラスコに加え、さらにメタノール(80mL)を加え、−25℃に冷却した。さらに酸化銀2.1g(9.06mmol)を加え、−25℃で6時間攪拌した。溶液を−25℃に保ったまま濾過を行って固体分をろ別し、ろ液部を減圧下で濃縮することで化合物16を4.1g(8.56mmol、収率97%)得た。
1H−NMR(500MHz、重DMSO):δ=7.82(d,J=7.5Hz,2H)、7.71(d,J=7.5Hz,2H)、7.41(t,J=7.5Hz,2H)、7.37(t,J=7.5Hz,2H)、4.63(m,4H)、3.98(s,6H)、3.19(m,4H)。
前記で製造した化合物16を3.89g(8.12mmol)、窒素雰囲気下の500mL3つ口フラスコに加え、さらにアセトニトリル(190mL)を加え、50℃に加熱した。さらにカルボニルクロロヒドリドトリス(トリフェニルホスフィン)ルテニウム(II)7.48g(8.08mmol)を加え、50℃で3時間攪拌した。放冷後、固体分をろ別し、ろ液部を減圧下で濃縮した。濃縮残渣にジクロロメタン(30mL)を加えて、溶液をヘキサン(300mL)に注ぎ、生じる固体部をろ取した。この固体をジクロロメタン/ヘキサンで再結晶することにより目的のルテニウム錯体3を2.5g(3.27mmol、収率40%)得た。ここでは、前記工程においてろ液を濃縮してから行ったが、濃縮せずにそのまま用いた場合も、同様にルテニウム錯体3が得られた。
1H−NMR(500MHz、重DMSO):δ=CD2Cl2):δ=7.5−7.2(m,19H)、6.91(t,J=7.5Hz,2H)、6.88(t,J=7.5Hz,2H)、4.94(t,J=5.8Hz,1H)、4.56(d,J=5.8Hz,1H)、4.45(d,J=5.8Hz,1H)、4.05(s,6H)、3.31br,1H,N−H)、3.3−3.1(m,4H)、2,87(d,J=5.8Hz,1H)、2.36(m,3H)、−7.52(d,2JPH=23.3Hz,1H)
13C―NMR(150MHz、重DMSO):δ=209(d,Ru−CO)。
アルドリッチ社より購入したジクロロビス[2−(ジフェニルホスフィノ)エタンアミン]ルテニウムを錯体4としてそのまま使用した。
特許文献2中に記載されたWO02/40115のRautenstrauch,V.等の記載に従って配位子:
ストレム社より購入したカルボニルクロロヒドリド[ビス(2−ジフェニルホスフィノエチル)アミノ]ルテニウムを錯体6としてそのまま使用した。
ストレム社より購入したカルボニルヒドリド[6−(ジ−t−ブチルホスフィノメチレン)−2−(N,N−ジエチルアミノメチル)−1,6−ジヒドロピリジン]ルテニウムを錯体7としてそのまま使用した。
特許文献5の実施例10の合成法に従い、下記イミダゾイリウム塩(1−[(2,4,6−トリメチルフェニル)メチル]−3−(3−アミノプロピル)イミダゾリウムクロライド):
非特許文献1に従い、非特許文献1に記載の化合物2aを錯体9として合成した。
次の反応式:
によりピバル酸メチルの水素化を行った。
実施例2−1において、錯体1の代わりに実施例1−2の錯体2(0.0113mmol)を用いた以外は、実施例2−1と同様にしてピバル酸メチルの水素化を実施した。
実施例2−1において、錯体1の代わりに実施例1−3の錯体3(0.0113mmol)を用いた以外は、実施例2−1と同様にしてピバル酸メチルの水素化を実施した。
実施例2−1において、錯体1の代わりに比較例1−1の錯体4(0.0113mmol)を用いた以外は、実施例2−1と同様にしてピバル酸メチルの水素化を実施した。
実施例2−1において、錯体1の代わりに比較例1−2の錯体5(0.0113mmol)を用いた以外は、実施例2−1と同様にしてピバル酸メチルの水素化を実施した。
実施例2−1において、錯体1の代わりに比較例1−3の錯体6(0.0113mmol)を用いた以外は、実施例2−1と同様にしてピバル酸メチルの水素化を実施した。
実施例2−1において、錯体1の代わりに比較例1−4の錯体7(0.0113mmol)を用い、かつ1Mカリウム−tert−ブトキシドのテトラヒドロフラン溶液(0.57mL)を加えなかった以外は、実施例2−1と同様にしてピバル酸メチルの水素化を実施した。
実施例2−1において、錯体1の代わりに比較例1−5の錯体8(0.0113mmol)を用いた以外は、実施例2−1と同様にしてピバル酸メチルの水素化を実施した。
実施例2−1において、錯体1の代わりに比較例1−6の錯体9(0.0113mmol)を用いた以外は、実施例2−1と同様にしてピバル酸メチルの水素化を実施した。
次の反応式:
により安息香酸メチルの水素化を行った。
次の反応式:
次の反応式:
Claims (16)
- 3座アミノジカルベン配位子と、ルテニウムイオン又はオスミニウムイオンとを有する金属錯体であって、前記3座アミノジカルベン配位子が、下記一般式(1):
で表される複素環カルベン基を表す。]
で表される配位子である、金属錯体。 - 前記R1〜R3は同一又は異なって、それぞれ独立に、水素原子、ハロゲン原子、又は置換基を有していてもよいアルキル基、シクロアルキル基、アリール基、複素環基、アルコキシ基、若しくはアリールオキシ基であるか、或いはR1とR2及び/又はR2とR3が一緒になって、置換基を有していてもよいアルキレン基、アルケニレン基、又はオキシアルキレン基を形成しており、且つ、前記R4〜R8は同一又は異なって、それぞれ独立に、水素原子、ハロゲン原子、又は置換基を有していてもよいアルキル基、シクロアルキル基、アリール基、複素環基、アルコキシ基、若しくはアリールオキシ基であるか、或いはR5とR6及び/又はR7とR8が一緒になって、置換基を有していてもよいアルキレン基、アルケニレン基又はオキシアルキレン基を形成している、請求項1に記載の金属錯体。
- 前記Q1及びQ2は同一であり、いずれもメチレン基、エチレン基又はプロピレン基である、請求項1又は2に記載の金属錯体。
- 前記一般式L1におけるR3が置換基を有してもよいアルキル基であり、一般式L2におけるR8が置換基を有してもよいアルキル基である、請求項1〜3のいずれかに記載の金属錯体。
- 前記一般式L1におけるR3が置換基を有してもよい直鎖状のアルキル基であり、一般式L2におけるR8が置換基を有してもよい直鎖状のアルキル基である、請求項1〜4のいずれかに記載の金属錯体。
- 前記一般式(1)における2個のLが共にL 1 である、請求項1〜5のいずれかに記載の金属錯体。
- 下記一般式(2)又は(3):
[M(A)Y1Y2Z1] ・・・(2)
[M(A)Y1Z1Z2]Y2 ・・・(3)
[式中、Mはルテニウムイオン又はオスミニウムイオン;Aは前記3座アミノジカルベン配位子;Y1及びY2は同一又は異なって、それぞれ1価のアニオン性配位子;Z1及びZ2は同一又は異なって、それぞれ単座配位子である。]
で表される組成を有する、請求項1〜6のいずれかに記載の金属錯体。 - 前記単座配位子は、CO、PR1aR1bR1c(R1a、R1b及びR1cは同一又は異なって、それぞれ置換基を有していてもよいアルキル基、シクロアルキル基、アリール基又は複素環基)、P(OR2a)(OR2b)(OR2c)(R2a、R2b及びR2cは同一又は異なって、それぞれ置換基を有していてもよいアルキル基、シクロアルキル基、アリール基又は複素環基)、SR3aR3b(R3a及びR3bは同一又は異なって、それぞれ置換基を有していてもよいアルキル基、シクロアルキル基、アリール基又は複素環基)、ニトリル基、イソニトリル基、N2、PF3、CS、テトラヒドロチオフェン又は炭素数1〜5のアルケンである、請求項7に記載の金属錯体。
- 前記一般式(2)及び(3)におけるY1及びY2のうち少なくとも一方がハロゲンイオンである、請求項7又は8に記載の金属錯体。
- 水素供与体を用いてカルボニル化合物又はイミン類を還元する反応の還元触媒として使用される、請求項1〜9のいずれかに記載の金属錯体。
- 金属錯体の製造方法であって、
アミノジカルベン前駆体(I)に金属化合物(II)を反応させ、次いで、化合物(III)を反応させる工程を備え、
前記アミノジカルベン前駆体(I)は、
1つの2級アミン基と、
該アミン基を挟んで、下記一般式L1’又はL2’:
で表される2つの複素環基と
を有し、
前記金属化合物(II)は、コバルトイオン、ニッケルイオン、銅イオン、ロジウムイオン、パラジウムイオン又は銀イオンを有し、
前記化合物(III)は、下記一般式(4):
MY1Y2Zn ・・・(4)
[式中、Mはルテニウムイオン又はオスミニウムイオン;Y1及びY2は同一又は異なって、それぞれ1価のアニオン性配位子;Zは同一又は異なって、それぞれ単座配位子;nは2〜4の整数を表す。]
で表される、請求項1に記載の金属錯体の製造方法。 - 前記単座配位子は、CO、PR1aR1bR1c(R1a、R1b及びR1cは同一又は異なって、それぞれ置換基を有していてもよいアルキル基、シクロアルキル基、アリール基又は複素環基)、P(OR2a)(OR2b)(OR2c)(R2a、R2b及びR2cは同一又は異なって、それぞれ置換基を有していてもよいアルキル基、シクロアルキル基、アリール基又は複素環基)、SR3aR3b(R3a及びR3bは同一又は異なって、それぞれ置換基を有していてもよいアルキル基、シクロアルキル基、アリール基又は複素環基)、ニトリル基、イソニトリル基、N2、PF3、CS、テトラヒドロチオフェン又は炭素数1〜5のアルケンである、請求項11に記載の金属錯体の製造方法。
- 前記金属化合物(II)が含有する金属イオンが、銀イオンである請求項11又は12に記載の金属錯体の製造方法。
- 請求項1〜10のいずれかに記載の金属錯体の存在下、水素供与体を用いてカルボニル化合物又はイミン類を還元する工程を備える、
カルボニル化合物又はイミン類の水素化還元方法。 - 前記カルボニル化合物がケトン類、カルボン酸エステル類、ラクトン類、カルボン酸アミド類及びラクタム類から選ばれる少なくとも1種である、請求項14に記載の水素化還元方法。
- 請求項1〜10のいずれかに記載の金属錯体の存在下、水素供与体を用いてカルボニル化合物又はイミン類を還元する工程を備える、
水素化還元されたカルボニル化合物又はイミン類の製造方法。
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