JP5446264B2 - 高分子担持金属錯体触媒 - Google Patents
高分子担持金属錯体触媒 Download PDFInfo
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- JP5446264B2 JP5446264B2 JP2008526709A JP2008526709A JP5446264B2 JP 5446264 B2 JP5446264 B2 JP 5446264B2 JP 2008526709 A JP2008526709 A JP 2008526709A JP 2008526709 A JP2008526709 A JP 2008526709A JP 5446264 B2 JP5446264 B2 JP 5446264B2
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- 239000003054 catalyst Substances 0.000 title claims description 67
- 150000004696 coordination complex Chemical class 0.000 title claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 72
- 239000010948 rhodium Substances 0.000 claims description 41
- 239000003446 ligand Substances 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 25
- 125000001424 substituent group Chemical group 0.000 claims description 22
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229910052703 rhodium Inorganic materials 0.000 claims description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 15
- 125000005842 heteroatom Chemical group 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229920006037 cross link polymer Polymers 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
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- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 125000003282 alkyl amino group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
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- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 5
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims 10
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- 239000000243 solution Substances 0.000 description 42
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- YNWSXIWHOSSPCO-UHFFFAOYSA-N rhodium(2+) Chemical compound [Rh+2] YNWSXIWHOSSPCO-UHFFFAOYSA-N 0.000 description 32
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- CVHOEDXIKCCEHU-UHFFFAOYSA-N 1-ethenyl-4-[3-[(4-ethenylphenyl)methoxy]propoxymethyl]benzene Chemical compound C1=CC(C=C)=CC=C1COCCCOCC1=CC=C(C=C)C=C1 CVHOEDXIKCCEHU-UHFFFAOYSA-N 0.000 description 7
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
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- 229910052786 argon Inorganic materials 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- KTDUPTNKZXMAQY-PKHIMPSTSA-N methyl (3s)-3-methyl-2-oxo-3-phenyl-1h-indene-1-carboxylate Chemical compound C1([C@]2(C)C(=O)C(C3=CC=CC=C32)C(=O)OC)=CC=CC=C1 KTDUPTNKZXMAQY-PKHIMPSTSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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Description
ロジウム(II)カルベン中間体のカルベン炭素は非常に高い求電子性を示し、この中間体に基づく反応は多岐にわたる。例えば炭素−炭素多重結合への付加、C-H及びX-H (X = N, O, S, Se, Siなど)結合への挿入あるいはイリド形成を引き金とする転位及び付加環化反応などが知られている。いずれも触媒反応であり、炭素-炭素結合形成と同時に不斉炭素を創出する合成化学上重要な反応である(非特許文献1)。
Rh2(OAc)4は架橋配位子であるアセタートを配位子交換反応により容易に種々カルボキシラートやアミダートに置き換えることが可能であり、多様な性質を持つロジウム(II)錯体を合成する事ができる。例えば、Doyleらは不斉空間が固定された不斉アミダート錯体Rh2(5S-MEPY)4やRh2(4S-MPPIM)4等を開発した(非特許文献2)。本錯体はα-ジアゾアセタートあるいはα-ジアゾアセトアミドの分子内C-H挿入反応や分子内シクロプロパン化反応において高いエナンチオ選択性を示す。McKervey、Daviesらはアレーンスルホニルプロリナートを架橋配位子に組み込んだロジウム(II)カルボキシラート錯体を開発した。特にDaviesらが開発したRh2(S-DOSP)4はヘキサン中で行なうフェニルジアゾアセタートあるいはビニルジアゾアセタートの分子間C-H挿入反応や分子間シクロプロパン化反応において極めて高いエナンチオ選択性が実現する(非特許文献3)。
本発明者らは光学活性N-フタロイルアミノ酸を架橋配位子として組み込んだロジウム(II)カルボキシラート錯体を開発し、種々のα-ジアゾカルボニル化合物を基質とする分子内不斉C-H挿入反応やイリド形成を経る不斉付加環化・転移反応を報告している(非特許文献4)。
ロジウム(II)錯体の除去・回収及び再利用に関する解決策の一つとして、不溶性固相担体へのロジウム(II)錯体の担持が挙げられる。固相ロジウム(II)錯体を用いることで、生成物との容易な分離、高価なロジウム錯体の回収及び再利用、金属の浸出の回避が理論的には可能となる。例えばDoyleらは、可溶性ポリエチレンを組み込んだピロリジノン-5(S)-カルボキシラートを架橋配位子とするロジウム(II)アミダート錯体Rh2(S-PYCA)4を開発した。本錯体はα-ジアゾアセタートの分子内不斉C-H挿入反応において、良好な不斉収率を維持しつつ数回の再利用に成功している(非特許文献6)。また、Daviesらは二核ロジウム(II)錯体のアキシアル位が種々のルイス塩基性の軸配位子で占有されている性質に着目し、Rh2(S-DOSP)4をはじめとする種々のロジウム(II)錯体に固相上のピリジンを配位することで担持する方法論を提示した。フェニルジアゾアセタートの分子間不斉C-H挿入反応において、固定化Rh2(S-DOSP)4触媒は、Rh2(S-DOSP)4単独で用いた場合と同等の触媒活性及び不斉識別能を示すことを見出している(非特許文献7)。一方、Biffisらはペルフルオロアルキル鎖を組み込んだシリカゲルにロジウム(II)ペルフルオロカルボキシラート錯体を保持した触媒を開発し、アルコールのシリル化反応における触媒の回収、再利用を実現している(非特許文献8)。
本発明者らは、多くのジアゾ分解反応で高い触媒活性及び不斉識別能を示す光学活性N-フタロイルアミノ酸を架橋配位子として組み込んだロジウム(II)カルボキシラート錯体を不溶性高分子に担持した固相触媒の開発について検討した。
(R4CXO)nM1M2
(式中、R4、X、n、M1及びM2は上記の定義のとおりである。)で表される錯体との配位子交換により形成されることを特徴とする高分子担持金属錯体触媒である。
まず、配位子として機能するポリマー部分を合成する。このポリマーは以下のようなモノマーを共重合することにより得ることができる。
(1)下記一般式(化2)で表される配位性モノマー
Xは酸素原子、硫黄原子又は=NR5基(式中、R5は水素原子又はアルキル基、好ましくは水素原子を表す。)、好ましくは酸素原子を表す。
このビニル基炭素には任意に置換基が結合していてもよい。このような置換基として、α位にメチル基などのアルキル基、アルキルオキシ基などが挙げられる。
この配位性モノマーとして、例えば、N-4-[6-(4-ビニルベンジルオキシ)ヘキシル]オキシフタロイル-(S)-tert-ロイシン、N-4-[6-(4-ビニルベンジルオキシ)ヘキシル]オキシフタロイル-(S)-フェニルアラニン、6-ヘキセン酸等が例示される。
このビニル基炭素には任意に置換基が結合していてもよい。このような置換基として、メチル基、エチル基、フェニル基、メトキシ基などが挙げられる。
この疎水性モノマーとして、スチレン、4-メチルスチレン、α-メチルスチレン、β-メチルスチレン、スチルベン、ビニルナフタレン等が例示される。
このビニル基炭素には任意に置換基が結合していてもよい。このような置換基として、
メチル基、エチル基、フェニル基などが挙げられる。
oは0〜4の整数、好ましくは0又は1を表し、pは1〜12の整数、好ましくは3〜8の整数、より好ましくは4〜6の整数表し、qは0〜4の整数、好ましくは0又は1を表し、rは0〜20の整数、好ましくは1〜2の整数を表す。
この重合性モノマーとして、1,3-ビス(4-ビニルベンジルオキシ)プロパン、1,4-ビス(4-ビニルベンジルオキシ)ブタン又は1,4-ジビニルベンゼンが例示される。
濃度は20〜50 wt%で行なうが、できるだけ高濃度で行なうことが望ましい。
重合開始剤はアゾビスイソブチロニトリル、過酸化ベンゾイル、tert-ブチルヒドロペルオキシド、過酸化水素-鉄(II)塩又は過酸化水素-トリエチルアルミニウム等が用いられる。反応温度は0℃から溶媒の還流温度の間で選ばれるが、好ましくは70℃付近である。
反応時間は反応温度及びモノマーの組成により異なるが、1〜96時間の間で適宜選択される。
この錯体は、下記一般式(化5)で表される。
(R4CXO)nM1M2
M1とM2は、同じであっても異なってもよく、ロジウム、パラジウム、ルテニウム、レニウム、鉄、ニッケル、銅、白金、ビスマス、コバルト、クロム、モリブデン及びタングステンから成る群から選択され、好ましくはロジウム、ルテニウム、クロム、モリブデン、タングステン又は銅を表す。
Xは上記の定義のとおりであり、
R4は置換基を有していてもよいアルキル基、アリール基、アラルキル基、アルキルオキシ基又はアルキルアミノ基、好ましくはアルキル基又はアミノアルキル基を表す。
nはM1とM2の原子価によって定まる整数であって、2〜4の整数を表す。例えばM1とM2がともにロジウム(II)又はルテニウム(II)又は銅(II)の場合はn=4となる。
このような錯体として、Rh2(S-PTTL)4、Rh2(O2CCH3)4が例示される。
本反応で用いられる溶媒はクロロベンゼンやトルエン、キシレン等の炭化水素系溶媒が用いられるが、クロロベンゼンの使用が望ましい。
反応は約100℃から溶媒の沸点までの範囲の温度で行なう。
反応時間はロジウム(II)錯体の進行の程度で選択されるが、1-9時間かけて行なう。通常は9時間行なった後一度反応溶液を洗浄し、再度ロジウム(II)錯体の溶液を加え加熱するサイクルを2-3回繰り返す。この方法により高分子に含まれるカルボキシル基の約50%が金属錯体に配位する。
すなわち、錯体と配位性モノマー(リンカーに結合する配位子)との等モル混合物を加熱(クロロベンゼンやトルエン、キシレン等の高沸点の溶媒中、110-130℃で加熱する)することで配位子交換を行ない、フェノール性水酸基に適当な長さの側鎖(末端にビニルフェニル基を組み込む必要があるが、その置換基と錯体の間は置換基がついていてもいなくてもよいアルキル基)を導入後、疎水性モノマー(スチレン)と重合性モノマー(1,3-ビス(4-ビニルベンジルオキシ)プロパン)を共重合させることによっても合成可能である。
この場合、先に示した共重合法の他に、アラビアゴム−食塩の水溶液に錯体−疎水性モノマー(スチレン)−重合性モノマー(1,3-ビス(4-ビニルベンジルオキシ)プロパン)のクロロベンゼン溶液を懸濁させ激しく撹拌しながら共重合させることも可能であり、この場合は任意の粒径をもつビーズ状の触媒を調製することも可能である。
この方法ははじめのロジウム(II)錯体を調製する段階においては低収率(未反応の可溶性ロジウム錯体Rh2(S-PTTL)4は原理的には回収再利用可能である)であるものの、重合直前まで金属錯体の構造を確認できる点及び原理的には高分子に含まれる全てのカルボキシル基が金属に配位していることになる(高分子触媒中に遊離のカルボキシル基が存在しない)。
これらの反応をジクロロメタン、1,2-ジクロロエタンやクロロホルム等のハロゲン化炭化水素溶媒、トルエン、ベンゼン、ベンゾトリフルオリド、キシレン等の芳香族炭化水素溶媒、エーテル、テトラヒドロフラン、メチルtert-ブチルエーテル、メチルシクロペンチルエーテル等のエーテル系溶媒、酢酸エチル、酢酸メチル等のエステル系溶媒、ヘキサン、ペンタン等の炭化水素系溶媒、エタノールやメタノール等のアルコール系溶媒、アセトニトリルやプロピオニトリル等のニトリル系溶媒、ニトロメタンやニトロエタン等のニトロアルカン系溶媒中で行なうことができる。
本触媒を用いることができる温度範囲は-78〜130℃であり、行なう反応の種類と基質・反応剤の活性によって最適温度を選択できる。
本触媒を用いる反応は、反応完結後反応混合物からろ過により不溶性の触媒を除くことができる。瀘取した触媒は適当な有機溶媒を用い数回洗浄した後、減圧下溶媒を留去することで再利用することが可能である。
以下、実施例にて本発明を例証するが本発明を限定することを意図するものではない。
TLC Rf 0.52(9:1 CH2Cl2/MeOH); [α]D -41.0°(c 1.08, CDCl3); IR(KBr)ν3474, 2963, 1956, 1777, 1716, 1616, 1485, 1370, 1278 cm-1; 1H NMR (270 MHz, CDCl3) δ1.17 (s, 9H, C(CH 3)3), 4.70 (s, 1H, CH(t-Bu)CO2H), 5.19 (s, 2H, OCH 2Ar), 7.24 (m, 1H, ArH), 7.40 (m, 6H, ArH), 7.77 (m, 1 H, ArH); 13C NMR (100.4 MHz,CDCl3)δ;28.1 (CH3), 35.7 (C), 60.0 (CH), 70.8 (CH2), 109.0 (CH), 121.0 (CH), 123.6 (C), 125.3 (CH), 127.4 (CH), 128.4 (CH), 128.7 (CH), 134.1 (C), 135.3 (C), 163.8 (C), 167.5 (phth C=O), 167.6 (phthC=O), 173.1 (COOH).; LRMS (EI) m/z 367 (M+); HRMS (EI) calcd for C21H21NO5: 367.1419 found 367.1416. Anal. Calcd for C21H21NO5: C, 68.65; H, 5.76; N, 3.81. Found: C, 68.66; H, 5.76; N, 3.83.
生成物の鏡像体過剰率(ee)は、ジアゾメタン処理してメチルエステルに導いた後キラルカラムを用いたHPLC分析により>99% eeと決定した。分析条件:column: Daicel Chiralcel OD-H; eluent: 19 : 1 hexane/2-propanol; flow: 1.0 mL/min; detection: 254 nm; retention time: 13.1 min (minor enantiomer R), 20.5 min (major enantiomer S).
TLC Rf 0.43 (5:1 hexane/EtOAc); [α]D -7.8°(c 0.78, EtOH); IR (KBr)ν3474, 2973, 1775, 1717, 1618, 1487, 1373, 1284 cm-1; 1H NMR (270 MHz, CDCl3) δ1.17 (s, 9H, C(CH 3)3), 1.40 (s, 9H, C(CH 3)3), 4.55 (s, 1H, CH(t-Bu)CO2t-Bu), 5.19 (s, 2H, OCH 2Ar), 7.23 (m, 1H, ArH), 7.42 (m, 6 H, ArH) 7.76 (m, 1H, ArH); 13C NMR (67.8 MHz, CDCl3)δ;27.9 (CH3), 28.1 (CH3), 35.6 (C), 60.7 (CH), 70.7 (CH2), 81.9 (C), 108.8 (CH), 120.7 (CH), 123.9 (C), 125.1 (CH), 127.5 (CH), 128.5 (CH), 128.8 (CH), 134.3 (C), 135.4 (C), 163.8 (C), 166.9 (C=O), 167.8 (C=O), 167.9 (C=O); LRMS (EI) m/z 423 (M+); HRMS (EI) calcd for C25H29NO5: 423.2045 found 423.2050; Anal. Calcd for C25H29NO5: C, 70.90; H, 6.90; N, 3.31. Found: C, 70.83; H, 6.91; N 3.21.
生成物の鏡像体過剰率(ee)は、キラルカラムを用いたHPLC分析により>99% eeと決定した。分析条件:column: Daicel Chiralcel OD-H; eluent: 19 : 1 hexane/2-propanol; flow: 1.0 mL/min; detection: 254 nm; retention time: 11.8 min (minor enantiomer R), 18.8 min (major enantiomer S).
TLC Rf 0.55(1:1 hexane/AcOEt); [α]D +1.1°(c 0.75, CDCl3); IR (KBr)ν3387, 2975, 1775, 1717, 1615, 1468, 1370, 1261 cm-1; 1H NMR (270 MHz, CDCl3) δ1.17 (s, 9H, C(CH 3)3), 1.40 (s, 9H, C(CH 3)3), 4,57 (s, 1H, CH(t-Bu)CO2 t-Bu), 7.08 (m, 1H, Ar), 7.25 (m, 1 H, Ar), 7.67 (m, 1 H, Ar); 13C NMR (100.4 MHz, CDCl3)δ;28.0 (CH3), 28.4 (CH3), 35.7 (C), 61.2 (CH), 83.0 (C), 110.7 (CH), 120.7 (CH), 122.8 (C), 125.5 (CH), 134.2 (C), 162.0 (C), 167.7 (C), 168.1 (C); LRMS (EI) m/z 334 (MH+); Anal. Calcd for C18H23NO5: C, 64.85; H, 6.95; N, 4.20. Found: C, 64.94; H, 7.01; N, 4.22.
TLC Rf 0.44 (1:1 hexane/EtOAc); IR (film)ν3403, 2935, 2858, 1630, 1512, 1406, 1364 cm-1; 1H NMR (270 MHz, CDCl3) δ1.22 (br, 1H, OH), 1.38 (m, 4H, -CH2-), 1.61 (m, 4H, -CH2-) 3.46 (t, J=5.94 Hz, 2H, OCH 2CH2), 3.63 (m, 2H, CH2CH 2OH), 4.49 (s, 2H, ArCH 2O), 5.23 (d, J = 11.2 Hz, 1H, ArCH=CH 2), 5.74 (d, J = 17.8 Hz, 1H, ArCH=CH 2), 6.71 (dd, J = 11.2 Hz, 17.8 Hz, 1H, ArCH=CH2), 7.29 (m, 2H, ArH), 7.39 (m, 2H, ArH); 13C NMR (100.4 MHz, CDCl3) δ25.6 (CH2), 26.0 (CH2), 29.7 (CH2), 32.7 (CH2), 62.7 (CH2), 70.2 (CH2), 72.5 (CH2), 113.5 (CH2), 126.0 (CH), 127.7 (CH), 136.4 (CH), 136.7 (C), 138.1 (C); LRMS (EI) m/z 234 (M+); HRMS (EI) m/z calcd for C15H22O2: 234.1620 found 234.1618. Anal. Calcd for C15H22O2: C, 76.88; H, 9.46. Found: C, 76.45; H, 9.42.
TLC Rf = 0.43 (3:1 hexane/AcOEt); IR (film)ν2938, 2861, 1630, 1599, 1512, 1402, 1360, 1177 cm-1; 1H NMR (270 MHz, CDCl3) δ1.29-1.34 (m, 4H, -CH 2-), 1.53-1.64 (m, 4H, -CH 2-), 2.44 (s, 3H, ArCH 3), 3.41 (t, J = 6.40 Hz, 2H, OCH 2CH2), 4.01 (t, J = 6.40 Hz, 2H, ArCH 2O), 4.46 (s, 2H, CH2CH 2OTs), 5.22 (d, J = 10.9 Hz, 1 H, ArCH=CH 2), 5.73 (d, J=16.9 Hz, 1 H, ArCH=CH 2), 6.70 (dd, J = 10.9 Hz, 16.9 Hz, 1 H, ArCH=CH2), 7.20 (m, 2H, ArH), 7.34 (m, 4H, ArH), 7.78 (m, 2H, ArH); 13C NMR (100.4 MHz, CDCl3) δ25.2 (CH2), 25.6 (CH2), 28.8 (CH2), 21.5 (CH3), 29.4 (CH2), 70.0 (CH2), 70.5 (CH2), 72.5 (CH2), 113.6 (CH2), 126.1 (CH), 127.7 (CH), 129.7 (CH), 133.1 (C), 136.4 (CH), 136.7 (C), 138.1 (C), 144.5 (C).; MS (EI) m/z 388 (M+); HRMS (EI) m/z calcd for C22H28SO4: 388.1708, found 388.1708. Anal. Calcd for C22H28 SO4: C, 68.01; H, 7.26; S, 8.25. Found: C, 67.16; H, 7.20; S, 8.19.
TLC Rf 0.43 (5:1 hexane/EtOAc); [α]D +1.7°(c 1.10, CHCl3); IR (film)ν3474, 2938, 2865, 1775, 1744, 1717, 1618, 1489, 1373 cm-1; 1H NMR (270 MHz, CDCl3) δ1.17 (s, 9H, C(CH 3)3), 1.40 (s, 9H, C(CH 3)3), 1.48 (m, 4H, -CH 2-), 1.66 (m, 2H, -CH 2-), 1.81 (m, 2H, -CH 2-), 3.48 (t, J = 6.6 Hz, 2H, OCH 2CH2), 4.06 (t, J = 6.6 Hz, 2H, OCH 2CH2), 4.49 (s, 2H, OCH 2Ar), 4.55 (s, 1H, CH(t-Bu)CO2t-Bu), 5.23 (d, J = 11.2 Hz, 1H, ArCH=CH 2), 5.74 (d, J = 17.8 Hz, 1H, ArCH=CH 2), 6.71 (dd, J = 11.2 Hz, 17.8 Hz, ArCH=CH2), 7.15 (m, 1H, ArH), 7.24 (m, 3 H, ArH), 7.39 (m, 2 H, ArH) 7.74 (m, 1 H, ArH); 13C NMR (67.8 MHz,CDCl3) δ25.8(CH2), 25.9 (CH2), 27.9 (CH3), 28.0 (CH3), 28.9 (CH2), 29.7 (CH2), 35.6 (C), 60.8 (CH), 68.8 (CH2), 70.1 (CH2), 72.6 (CH2), 81.8 (C), 108.2 (CH), 113.6 (CH2), 120.3 (CH), 123.3 (C), 125.0 (CH), 126.1 (CH), 127.7 (CH), 134.2 (C), 136.4 (CH), 136.7 (C), 138.1 (C), 164.1 (C), 166.7 (C=O), 167.7 (C=O), 167.8 (C=O); LRMS (EI) m/z 549 (M+); HRMS (EI) calcd for C33H43NO6: 549.3090, found 549.3097; Anal. Calcd for C33H43NO6: C, 72.10; H, 7.88; N 2.55. Found: C, 70.74; H, 7.89; N, 2.49.
生成物の鏡像体過剰率(ee)は、キラルカラムを用いたHPLC分析により>99% eeと決定した。分析条件:column: Daicel Chiralcel OJ-H; eluent: 19 : 1 hexane/2-propanol; flow: 1.0 mL/min; detection: 254 nm; retention time: 9.7 min (minor enantiomer R), 16.3 min (major enantiomer S).
TLC Rf 0.50 (9:1 CH2Cl2/MeOH); [α]D -14.9° (c 0.56, CHCl3); IR (film)ν2940, 2866, 1775, 1714, 1618, 1489, 1450, 1375 cm-1; 1H NMR (270 MHz, CDCl3) δ1.17 (s, 9H, C(CH 3)3), 1.46 (m, 4H, -CH 2-), 1.64 (m, 2H, -CH 2-), 1.82 (m, 2H, -CH 2-), 3.47 (t, J = 6.4 Hz, 2H, OCH 2CH2), 4.05 (t, J = 6.4 Hz, 2H, OCH 2CH2), 4.49 (s, 2H, OCH 2Ar), 4.69 (s, 1H, CH(t-Bu)CO2H), 5.23 (d, J = 10.9 Hz, 1H, ArCH=CH 2), 5.74 (d, J = 17.5 Hz, 1H, ArCH=CH 2), 6.70 (dd, J = 10.9 Hz, 17.5 Hz, ArCH=CH2), 7.14 (m, 1H, ArH), 7.29 (m, 3H, ArH), 7.38 (m, 2H, ArH) 7.74 (m, 1H, ArH); 13C NMR (67.8 MHz, CDCl3) δ25.8(CH2), 25.9 (CH2), 28.0 (CH3), 28.9 (CH2), 29.6 (CH2), 35.7 (C), 59.9 (CH), 68.9 (CH2), 70.1 (CH2), 72.6 (CH2), 108.5 (CH), 113.6 (CH2), 120.6 (CH), 123.1 (C), 125.2 (CH), 126.1 (CH), 127.8 (CH), 134.1 (C), 136.4 (CH), 136.8 (C), 138.0 (C), 164.3 (C), 166.7 (C=O), 167.8 (C=O), 172.7 (C=O); MS (EI) m/z 493 (M+); HRMS (EI) m/z calcd for C29H35NO6: 493.2464 found 493.2464.
生成物の鏡像体過剰率(ee)は、ジアゾメタン処理してメチルエステルに導いた後キラルカラムを用いたHPLC分析により>99% eeと決定した。分析条件:column: Daicel Chiralcel OJ-H; eluent: 19 : 1 hexane/2-propanol; flow: 1.0 mL/min; detection: 254 nm; retention time: 11.3 min (minor enantiomer R), 16.9 min (major enantiomer S).
TLC Rf = 0.40 (19:1 hexane/EtOAc); IR (film)ν2859, 1630, 1510, 1404, 1364 cm-1; 1H NMR (270 MHz, CDCl3) δ1.91 (t, J = 6.2 Hz, 2H, CH 2CH2O), 3.57 (t, J = 6.2 Hz, 4H, CH2CH 2O), 4.58 (s, 4H, ArCH 2O), 5.23 (d, J = 10.7 Hz, 2 H, ArCH=CH 2), 5.73 (d, J = 17.7 Hz, 2 H, ArCH=CH 2), 6.70 (dd, J = 10.7 Hz, 17.7 Hz, 2 H, ArCH=CH2), 7.26 (m, 4H, ArH), 7.37 (m, 4H, ArH); 13C NMR (67.8 MHz, CDCl3) δ30.2 (CH2), 67.3 (CH2), 72.7 (CH2), 113.6 (CH2), 126.1 (CH), 127.8 (CH), 136.5 (CH), 136.8 (C), 138.1 (C); Anal. Calcd for C21H24O2: C, 81.78; H, 7.84. Found: C, 81.61; H, 7.94.
N-4-[6-(4-ビニルベンジルオキシ)ヘキシル]オキシフタロイル-(S)-tert-ロイシン(49.4 mg, 0.1 mmol)、スチレン(194 mg, 1.86 mmol)、1,3-ビス(4-ビニルベンジルオキシ)プロパン(12.3 mg, 0.04 mmol)及びAIBN(3.2 mg, 0.02 mmmol)のtert-ブチルアルコール溶液(1 mL)をアルゴン雰囲気下、3回のfreeze-pump-thaw操作で脱気した後、70℃で60時間撹拌した。反応溶液を濃縮後、粗生成物 (260 mg)をジクロロメタン(5 mL)及び酢酸エチル(3×5mL)で順次洗浄し、残渣を減圧乾燥し高分子配位子(123 mg, 48%)を白色粉末として得た。生成物の分析データを以下に記す。
Anal. Calcd for C950H990N6O40 : C, 86.89; H, 7.60; N, 0.64. Found: C, 86.99; H, 7.67; N, 0.69.
Anal. Calcd for C1100H1161N15O82Rh6: C, 79.97; H, 7.08; N, 1.27; Rh, 3.74. Found: C, 79.61; H, 7.02; N, 1.28; Rh, 3.54. この結果より、理論値の50%の二核ロジウム(II)錯体が高分子配位子に取り込まれたことになる。
N-4-ヒドロキシフタロイル-(S)-tert-ロイシンの機器データを以下に記す。
TLC Rf 0.41 (9:1 CH2Cl2/MeOH); 1H NMR (400 MHz, CD3OD) δ 1.13 (s, 9H, C(CH 3)3), 4,53 (s, 1H, CH(t-Bu)CO2H), 7.11 (dd, J=2.2 Hz, J=8.2 Hz, 1H, Ar), 7.18 (d, J=2.2 Hz, 1 H, Ar), 7.69 (d, dd, J=8.2 Hz, 1H, Ar); 13C NMR (100.4 MHz, CD3OD) δ ; 28.4 (CH3), 36.3 (C), 60.6 (CH) 110.9 (CH), 121.7 (CH), 123.2 (C), 126.3 (CH), 135.5 (C), 165.0 (C), 169.4(C), 169.4(C), 170.9 (C); LRMS (FAB) m/z 278 (M+H); HRMS (FAB) calcd for C14H16NO5: 278.1028 found 278.1029. Anal. Calcd for C14H15NO5: C 60.64, H 5.45, N 5.05, found C 60.79, H 5.51, N 5.03.
生成物の機器データを以下に記す。
TLC Rf 0.51 (1:2 hexane/AcOEt); mp >280℃; 1H NMR (270 MHz, CDCl3) δ 1.09 (s, 9H, C(CH3)3), 1.11 (br, 27H, C(CH3)3), 1.26 (t, J =7.26 Hz, 6H, CH3CH2), 2.05 (s, 6H, CH 3), 4.12 (q J =7.26 Hz, 4H, CH3CH2), 4.67 (s, 1H, CH(t-Bu)CO2), 4.80 (br, 3H, CH(t-Bu)CO2), 7.00 (m, 1H, Ar), 7.12 (m, 1H, Ar), 7.56-7.76 (m, 13 H, Ar); 13C NMR (100.4 MHz, CDCl3) δ 14.1 (CH3), 21.0 (CH3), 21.0 (CH3), 28.0 (CH3), 35.2 (C), 35.6, (C), 35.6 (C), 60.6 (CH2), 61.3 (CH), 110.1 (CH), 120.3 (CH), 123.2 (CH), 124.8 (CH), 131.7 (C), 131.8 (C), 133.8 (CH), 167.5 (C), 171.8 (C), 185.6(C), 186.7 (C), 187.0 (C); LRMS (FAB) m/z 1262 (M+); HRMS (FAB) calcd for C56H56N4O17Rh2: 1262.1751 found 1262.1753. Anal. Calcd for C56H56N4O17Rh2・2AcOEt: C 53.41, H 5.04, N 3.89. found C 53.66, H 5.21, N 4.07.
生成物の機器データを以下に記す。
TLC Rf = 0.53 (10:1 hexane/AcOEt); 1H NMR (270 MHz, CDCl3) δ 1.37-1.48 (m, 4H, -(CH2)-), 1.51-1.65 (m, 2H, -(CH2)-), 1.81-1.91 (m, 2H, -(CH2)-), 3.38-3.48 (m, 4H, OCH2CH2, BrCH2CH2), 4.49 (s, OCH2Ar), 5.23 (d, J=10.9 Hz, 1 H, ArCHCH2), 5.74 (d, J=17.5 Hz, 1 H, ArCHCH2), 6.71 (dd, J=10.9 Hz, 17.5 Hz, 1 H, ArCHCH2), 7.28 (m, 2H, Ar), 7.39 (m, 2H, Ar); 13C NMR (100.4 MHz, CDCl3) δ 25.4 (CH2), 28.0 (CH2), 29.6 (CH2), 32.7 (CH2), 33.8 (CH2), 70.0 (CH2), 72.5 (CH2), 113.5(CH2), 126.0 (CH), 127.6 (CH), 136.4 (CH), 136.7 (C), 138.0 (C); MS (EI) m/z 296 (M+); HRMS (EI) m/z calcd for C15H21BrO: 296.0775 found 296.0778. Anal. Calcd for C15H21BrO: C 60.61, H 7.12, Br 26.88.; found C 60.79, H 7.22, S 26.83.
生成物の機器データを以下に記す。
TLC Rf 0.54 (1:1 hexane/EtOAc); 1H NMR (270 MHz, CDCl3) δ 1.02 (br, 36H, C(CH3)3), 1.18 (t, J=7.26 Hz, 6H, CH3CH2), 1.21, (m, 4H), 1.57 (m, 2H), 1.76 (m, 2H), 1.97 (s, 6H, CH 3), 3.40 (m, 2H), 4.00 (m, 2H), 4.12 (q J=7.26 Hz, 4H, CH3CH2), 4.40 (s, 2H), 4.64 (s, 1H, CH(t-Bu)CO2), 4.70 (br, 3H, CH(t-Bu)CO2), 5.16 (d, J=10.9 Hz, 1 H, ArCHCH2), 5.67 (d, J=16.9 Hz, 1 H, ArCHCH2), 6.71 (dd, J=10.9 Hz, 16.9 Hz, 1 H, ArCHCH2), 7.01 (m, 1H, Ar), 7.12 (m, 1H, Ar), 7.56-7.76 (m, 13 H, Ar); LRMS (FAB) m/z 1478 (M+); HRMS (FAB) calcd for C71H76N4O18Rh2: 1478.3265 found 1478.3258.
生成物の機器データは以下の通りである。
Anal. Calcd for C1141H1174N20O94Rh10・10AcOEt : C, 76.34; H, 6.80; N, 1.51; Rh, 5.54. anal; C, 76.80; H, 7.05; N, 1.50; Rh, 4.99.
(1S,2R)-2-フェニルシクロペンタンカルボン酸メチルの分析データを以下に記す。
TLC Rf 0.39 (5:1 hexane/EtOAc); IR (neat) ν 1732 (C=O), 1200, 1171, 700 cm-1; 1H NMR (400 MHz, CDCl3) δ 1.70 (m, 1H, CH 2), 1.95-2.15 (m, 5H, CH 2), 3.16 (ddd, J = 6.2, 9.0, 9.0 Hz, 1H, C2-H), 3.22 (s, 3H, CO2CH 3), 3.41 (ddd, J = 7.1, 9.0, 9.0 Hz, 1H, C1-H), 7.15-7.28 (m, 5H, ArH); 13C NMR (100 MHz, CDCl3) δ 24.8 (CH2), 28.6 (CH2), 31.2 (CH2), 49.2 (CH), 49.8 (CH), 50.9 (CH3), 126.3 (CH), 127.8 (CH), 127.9 (CH), 141.5 (C), 174.9 (C=O); LRMS (EI) m/z 204 (M+); HRMS (EI) calcd for C13H16O2 (M+) 204.1150; found 204.1151; Anal. Calcd for C13H16O2: C, 76.44; H, 7.90. Found: C, 76.33; H, 7.98.
鏡像異性体過剰率(ee)はキラルカラムを用いたHPLC分析により94%と決定した。分析条件: column Daicel Chiralcel OJ-H followed by Daicel Chiralpak AS-H; eluent: 100:1 hexane/i-PrOH; 1.0 mL/min; detection: 254 nm; retention time: 12.9 min for (1R,2S) enantiomer (minor), 14.7 min for (1S,2R) enantiomer (major).
TLC Rf 0.35 (5:1 hexane/EtOAc); mp 91-92℃; IR (neat) ν 1736 (C=O), 1480, 1229, 1213 cm-1; 1H NMR (270 MHz, CDCl3) δ 3.21 (s, 3H, CO2CH 3), 4.62 (d, J = 9.9 Hz, 1H, CH CO2CH3), 5.99 (d, J = 9.9 Hz, 1H, OCHPh), 6.01-6,98 (m, 2H, ArH), 7.22-7.38 (m, 2H, ArH); 13C NMR (67.8 MHz, CDCl3) δ 51.5 (CH3), 53.9 (CH), 85.6 (CH), 109.9 (CH), 121.2 (CH), 124.7 (C), 125.8 (CH), 126.1 (CH), 128.1 (CH), 128.2 (CH), 129.5 (CH), 137.0 (C), 160.4 (C), 170.2 (C=O); LRMS (EI) m/z 254 (M+); HRMS (EI) calcd for C16H14O3 (M+) 254.0943; found 254.0946; Anal. Calcd for C16H14O3: C, 75.57; H, 5.55. Found: C, 75.38; H, 5.77.
鏡像異性体過剰率(ee)はキラルカラムを用いたHPLC分析により89%と決定した。分析条件: column Daicel Chiralcel OD-H; eluent: 9:1 hexane/i-PrOH; 1.0 mL/min; detection: 254 nm; retention time: 7.9 min for (2R,3S) enantiomer (major), 14.1 min for (2S,3R) enantiomer (minoir).
実施例1で得た固相担持ロジウム(II)錯体(7.4 mg, 2 mol % of catalyst)及びジクロロメタン(0.5 mL)を入れた反応用試験管に2-ジアゾ-4,4-ジフェニル-3-オキソペンタン酸メチル(30.8 mg, 0.1 mmol)のジクロロメタン溶液(0.5 mL)を室温で加え、その温度で20 分間撹拌した。上清をデカンテーション後、残査をジクロロメタン(1 mL)で洗浄した。あわせた上清を濃縮後、残査 (28 mg)をカラムクロマトグラフィー (シリカゲル 1 g、ベンゼン)精製し(3S)-3-メチル-3-フェニル-2-オキソインダン-1-カルボン酸メチル(24.1 mg, 86%)を淡青色固体として得た。得られた(3S)-3-メチル-3-フェニル-2-オキソインダン-1-カルボン酸メチルの光学純度は、脱メトキシカルボニル化後のHPLC分析により91% eeであることが分かった。回収した固相担持ロジウム(II)錯体は、減圧乾燥後同様の反応を繰り返し行った。
(3S)-3-メチル-3-フェニル-2-オキソインダン-1-カルボン酸メチルの分析データを以下に記す。
TLC Rf 0.55 (2 : 1 hexane/EtOAc); mp 81.0-82.0℃; IR (KBr) ν 2971, 2949, 1595, 1475, 1440 cm-1; 1H NMR (270 MHz, CDCl3, almost enol form) δ 1.80 (3H, s, CH 3), 3.98 (3H, s, CO2CH 3), 7.07-7.13 (2H, m, ArH), 7.20-7.32 (6H, m, ArH), 7.65 (1H, d, J = 7.3 Hz, ArH), 11.00 (1H, brs, enol-OH); 13C NMR (67.8 MHz, CDCl3) δ 21.7 (CH3), 51.6 (CH3), 54.8 (C), 102.3 (C), 120.5 (CH), 122.8 (CH), 124.5 (CH), 126.6 (CH), 127.3 (CH), 127.4 (CH), 128.5 (CH), 137.5 (C), 140.2 (C), 145.0 (C), 169.5 (C), 186.2 (C); LRMS (EI) m/z 280 (M+), 248, 233, 219, 205, 192; HRMS (EI) calcd for C18H16O3 (M+) 280.1099, found 280.1092; Anal. Calcd for C18H16O3: C, 77.12; H, 5.75. Found: C, 77.33; H, 5.92.
(S)-3-メチル-3-フェニル-2-インダノンの分析データを以下に記す。
TLC Rf 0.65 (2 : 1 hexane/EtOAc); IR (film) ν 3025, 2971, 1752, 1597, 1495, 1480 cm-1; 1H NMR (270 MHz, CDCl3) δ 1.76 (3H, s, CH 3 ), 3.53 (1H, d, J = 21.8 Hz, CH 2), 3.68 (1H, d, J = 21.8 Hz, CH 2), 7.16-7.41 (9H, m, ArH); 13C NMR (67.8 MHz, CDCl3) ? 23.8 (CH3), 41.6 (CH2), 58.3 (C), 124.8 (CH), 125.2 (CH), 126.7 (CH), 126.9 (CH), 127.7 (CH), 127.9 (CH), 128.4 (CH), 135.8 (C), 142.0 (C), 146.4 (C), 216.1 (C); LRMS (EI) m/z 222 (M+), 194, 179, 165, 152; HRMS (EI) calcd for C16H14O (M+) 222.1045, found 222.1046; Anal. Calcd for C16H14O: C, 86.45; H, 6.35. Found: C, 86.40; H, 6.40.
生成物の鏡像体過剰率(ee)はキラルカラムを用いたHPLC分析により97% eeと決定した。
分析条件:column: Daicel Chiralcel OD-H; eluent: 200 : 1 hexane/2-propanol; flow: 1.0 mL/min; detection: 254 nm; retention time: 9.4 min (major enantiomer S), 10.8 min (minor enantiomer R).
Claims (8)
- 金属を架橋高分子に担持させてなる下式(化1)
(1)一般式(化2)
(2)該架橋高分子と下記一般式(化5)
(R4CXO)nM1M2
(式中、R4、X、n、M1及びM2は上記の定義のとおりである。)で表される錯体とを配位子交換させる段階
から成る方法により形成されることを特徴とする高分子担持金属錯体触媒。 - 分子内不斉C−H挿入反応又はカルボニルイリドの1,3-双極付加環化反応における請求項1又は2に記載の触媒の使用。
- 金属を架橋高分子に担持させてなる下式(化1)
(1)一般式(化21)
(R4CXO)nM1M2
(式中、R4、X、n、M1及びM2は上記の定義のとおりである。)で表される錯体との配位子交換により金属(M1及びM2)を該配位性化合物に担持させる段階、
(2)この金属を担持させた配位性化合物から、一般式(化22)
(3)上記化合物(化22)にビニル基を導入して、一般式(化23)
(4)当該金属を担持させた配位性モノマー、一般式(化3)
から成る方法により形成されることを特徴とする高分子担持金属錯体触媒。 - 分子内不斉C−H挿入反応又はカルボニルイリドの1,3-双極付加環化反応における請求項4に記載の触媒の使用。
- 金属を架橋高分子に担持させてなる下式(化1)
(1)一般式(化2)
(2)該架橋高分子と下記一般式(化5)
(R4CXO)nM1M2
(式中、R4、X、n、M1及びM2は上記の定義のとおりである。)で表される錯体とを配位子交換させる段階
から成る高分子担持金属錯体触媒の製法。 - 金属を架橋高分子に担持させてなる下式(化1)
(1)一般式(化21)
(R4CXO)nM1M2
(式中、R4、X、n、M1及びM2は上記の定義のとおりである。)で表される錯体との配位子交換により金属(M1及びM2)を該配位性化合物に担持させる段階、
(2)この金属を担持させた配位性化合物から、一般式(化22)
(3)上記化合物(化22)にビニル基を導入して、一般式(化23)
(4)当該金属を担持させた配位性モノマー、一般式(化3)
から成る高分子担持金属錯体触媒の製法。
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EP2045014B8 (en) | 2014-02-26 |
US8092720B2 (en) | 2012-01-10 |
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