東京化成工業株式会社｜光学純度，絶対配置決定用試薬

光学純度，絶対配置決定用試薬
Enantiomer Excess & Absolute Configuration
Determination

　医薬，農薬，液晶を始めとする機能性材料の研究，開発において光学活性物質の重要性が高まりつつあり，不斉合成，光学分割による光学活性物質の入手法が盛んに研究されています。そして，光学活性物質の入手法と同じく，あるいはそれ以上に光学活性物質の光学純度，絶対配置の決定法が研究されており，NMR^１），HPLC^２），CD励起子キラリティー法^３）に使用する優れた光学純度，絶対配置決定用試薬が開発されています。依馬らが開発したキラルシフト試薬キラバイト-AR （1）もこうした試薬の一つで，NMRを用いて簡便に光学純度を測定することができます^4）。

　キラバイト-AR (1)は大環状化合物で，1の空孔は水素結合ドナー部位と水素結合アクセプター部位が巧みな組合せで配置されており，その空孔内に幅広い化合物をゲスト分子として取り込みます。そして，取り込まれたゲスト分子は，不斉源であるBINOLの強い磁気異方性効果を受け，エナンチオマー間でそのケミカルシフト値が大きく異なります。

　近年，高磁場NMRが普及しつつあり，従来から用いられているEu錯体ではブロードニングが生じ，満足の行くNMRスペクトルを得ることができません。1はブロードニングの原因となる金属を含んでいないため，高磁場NMR，低磁場NMRのいずれにも利用でき，カルボン酸，オキサゾリジノン，炭酸エステル，ラクトン，アルコール，スルホキシド，スルホキシイミン，スルフィンアミド，イソシアナート，エポキシなどの幅広い化合物の光学純度が測定できます。また，その測定法は極めて簡便で，NMR試料管中の測定対象試料を溶解した重クロロホルムに1を添加するだけでエナンチオマー間のケミカルシフト値が異なるスペクトルを得ることができます。
　1は利用しやすいこと，適応化合物が広範なこと，低磁場NMRから高磁場NMRまで利用できることなど，従来のキラルシフト試薬を凌駕する性能を有します。

NMR測定用 / for NMR

M1339	M1103	B1720
M1104	B1721	C1021
D2176	D2459	A1657
N0713	D2460	D2175
A1658	N0714	N0482
P0794	M0831	I0334
B1143	I0336	T1520
M1366	P1219	M0830
D1852	D1853	B1161
B1144	I0398	T1521
M1367	P1220	M0829
N0481	P0793	M0832
I0335	B1343	C2184
M0662	M0661	S0473
S0474

M1339	(+)-alpha-Methoxy-alpha-(trifluoromethyl)phenylacetic Anhydride
M1103	(+)-alpha-Methoxy-alpha-(trifluoromethyl)phenylacetyl Chloride [for Determination of the optical purity of Alcohols and Amines]
B1720	(+)-Benzylmethylphenylsilylacetic Acid [for e.e. Determination by NMR]
M1104	(-)-alpha-Methoxy-alpha-(trifluoromethyl)phenylacetyl Chloride [for Determination of the optical purity of Alcohols and Amines]
B1721	(-)-Benzylmethylphenylsilylacetic Acid [for e.e. Determination by NMR]
C1021	(-)-Camphanic Acid
D2176	(1R,2R)-(+)-1,2-Diphenylethylenediamine
D2459	(1R,2R)-(-)-N,N'-Dimethylcyclohexane-1,2-diamine
A1657	(1R,2R)-2-(Anthracene-2,3-dicarboximido)cyclohexanecarboxylic Acid
N0713	(1R,2R)-2-(Naphthalene-2,3-dicarboximido)cyclohexanecarboxylic Acid
D2460	(1S,2S)-(+)-N,N'-Dimethylcyclohexane-1,2-diamine
D2175	(1S,2S)-(-)-1,2-Diphenylethylenediamine
A1658	(1S,2S)-2-(Anthracene-2,3-dicarboximido)cyclohexanecarboxylic Acid
N0714	(1S,2S)-2-(Naphthalene-2,3-dicarboximido)cyclohexanecarboxylic Acid
N0482	(R)-(+)-1-(1-Naphthyl)ethylamine
P0794	(R)-(+)-1-Phenylethylamine
M0831	(R)-(+)-alpha-Methoxy-alpha-(trifluoromethyl)phenylacetic Acid [Optical Resolving]
I0334	(R)-(+)-alpha-Methylbenzyl Isocyanate
B1143	(R)-(-)-1,1'-Binaphthyl-2,2'-diyl Hydrogen Phosphate
I0336	(R)-(-)-1-(1-Naphthyl)ethyl Isocyanate
T1520	(R)-(-)-2,2,2-Trifluoro-1-(9-anthryl)ethanol [e.e. Determination Reagent by NMR]
M1366	(R)-(-)-2-Methoxy-2-(1-naphthyl)propionic Acid
P1219	(R)-(-)-2-Phenylpropionic Acid
M0830	(R)-(-)-alpha-Methoxyphenylacetic Acid
D1852	(R)-(-)-N-(3,5-Dinitrobenzoyl)-alpha-phenylethylamine
D1853	(R)-(-)-N-(3,5-Dinitrobenzoyl)-alpha-phenylglycine
B1161	(R,R)-(-)-2,3-Butanediol
B1144	(S)-(+)-1,1'-Binaphthyl-2,2'-diyl Hydrogen Phosphate
I0398	(S)-(+)-1-(1-Naphthyl)ethyl Isocyanate
T1521	(S)-(+)-2,2,2-Trifluoro-1-(9-anthryl)ethanol [e.e. Determination Reagent by NMR]
M1367	(S)-(+)-2-Methoxy-2-(1-naphthyl)propionic Acid
P1220	(S)-(+)-2-Phenylpropionic Acid
M0829	(S)-(+)-alpha-Methoxyphenylacetic Acid
N0481	(S)-(-)-1-(1-Naphthyl)ethylamine
P0793	(S)-(-)-1-Phenylethylamine
M0832	(S)-(-)-alpha-Methoxy-alpha-(trifluoromethyl)phenylacetic Acid [Optical Resolving]
I0335	(S)-(-)-alpha-Methylbenzyl Isocyanate
B1343	(S,S)-(+)-2,3-Butanediol
C2184	Chirabite-AR
M0662	D-(-)-Mandelic Acid
M0661	L-(+)-Mandelic Acid
S0473	Sodium [(R)-1,2-Diaminopropane-N,N,N',N'-tetraacetato]samarate(III) Hydrate
S0474	Sodium [(S)-1,2-Diaminopropane-N,N,N',N'-tetraacetato]samarate(III)

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HPLC測定用 / for HPLC

A1657	N0713	A1658
N0714	I0334	A5565
A5566	I0336	M1366
A5561	A5568	A5563
A5577	I0398	M1367
A5560	A5569	A5562
A5578	I0335	A5564
A5567	A5514	A5515
A5524	D2259	A5523

A1657	(1R,2R)-2-(Anthracene-2,3-dicarboximido)cyclohexanecarboxylic Acid
N0713	(1R,2R)-2-(Naphthalene-2,3-dicarboximido)cyclohexanecarboxylic Acid
A1658	(1S,2S)-2-(Anthracene-2,3-dicarboximido)cyclohexanecarboxylic Acid
N0714	(1S,2S)-2-(Naphthalene-2,3-dicarboximido)cyclohexanecarboxylic Acid
I0334	(R)-(+)-alpha-Methylbenzyl Isocyanate
A5565	(R)-(+)-DBD-Pro-COCl [=(R)-(+)-4-(N,N-Dimethylaminosulfonyl)-7-(2-chloroformylpyrrolidin-1-yl)-2,1,3-benzoxadiazole] [HPLC Labeling Reagent for e.e. Determination]
A5566	(R)-(+)-NBD-Pro-COCl [=(R)-(+)-4-Nitro-7-(2-chloroformylpyrrolidin-1-yl)-2,1,3-benzoxadiazole] [HPLC Labeling Reagent for e.e. Determination]
I0336	(R)-(-)-1-(1-Naphthyl)ethyl Isocyanate
M1366	(R)-(-)-2-Methoxy-2-(1-naphthyl)propionic Acid
A5561	(R)-(-)-DBD-APy [=(R)-(-)-4-(N,N-Dimethylaminosulfonyl)-7-(3-aminopyrrolidin-1-yl)-2,1,3-benzoxadiazole] [HPLC Labeling Reagent for e.e. Determination]
A5568	(R)-(-)-DBD-Py-NCS [=(R)-(-)-4-(N,N-Dimethylaminosulfonyl)-7-(3-isothiocyanatopyrrolidin-1-yl)-2,1,3-benzoxadiazole] [for HPLC Labeling]
A5563	(R)-(-)-NBD-APy [=(R)-(-)-4-Nitro-7-(3-aminopyrrolidin-1-yl)-2,1,3-benzoxadiazole] [HPLC Labeling Reagent for e.e. Determination]
A5577	(R)-(-)-NBD-Py-NCS [=(R)-(-)-4-(3-Isothiocyanatopyrrolidin-1-yl)-7-nitro-2,1,3-benzoxadiazole] [HPLC Labeling Reagent for e.e. Determination]
I0398	(S)-(+)-1-(1-Naphthyl)ethyl Isocyanate
M1367	(S)-(+)-2-Methoxy-2-(1-naphthyl)propionic Acid
A5560	(S)-(+)-DBD-APy [=(S)-(+)-4-(N,N-Dimethylaminosulfonyl)-7-(3-aminopyrrolidin-1-yl)-2,1,3-benzoxadiazole] [HPLC Labeling Reagent for e.e. Determination]
A5569	(S)-(+)-DBD-Py-NCS [=(S)-(+)-4-(N,N-Dimethylaminosulfonyl)-7-(3-isothiocyanatopyrrolidin-1-yl)-2,1,3-benzoxadiazole] [for HPLC Labeling]
A5562	(S)-(+)-NBD-APy [=(S)-(+)-4-Nitro-7-(3-aminopyrrolidin-1-yl)-2,1,3-benzoxadiazole] [HPLC Labeling Reagent for e.e. Determination]
A5578	(S)-(+)-NBD-Py-NCS [=(S)-(+)-4-(3-Isothiocyanatopyrrolidin-1-yl)-7-nitro-2,1,3-benzoxadiazole] [HPLC Labeling Reagent for e.e. Determination]
I0335	(S)-(-)-alpha-Methylbenzyl Isocyanate
A5564	(S)-(-)-DBD-Pro-COCl [=(S)-(-)-4-(N,N-Dimethylaminosulfonyl)-7-(2-chloroformylpyrrolidin-1-yl)-2,1,3-benzoxadiazole] [HPLC Labeling Reagent for e.e. Determination]
A5567	(S)-(-)-NBD-Pro-COCl [=(S)-(-)-4-Nitro-7-(2-chloroformylpyrrolidin-1-yl)-2,1,3-benzoxadiazole] [HPLC Labeling Reagent for e.e. Determination]
A5514	2,3,4,6-Tetra-O-acetyl-beta-D-glucopyranosyl Isothiocyanate [for HPLC Labeling]
A5515	2,3,4,6-Tetra-O-benzoyl-beta-D-glucopyranosyl Isothiocyanate [for HPLC Labeling]
A5524	Nalpha-(5-Fluoro-2,4-dinitrophenyl)-D-leucinamide [HPLC Labeling Reagent for e.e. Determination]
D2259	Nalpha-(5-Fluoro-2,4-dinitrophenyl)-L-alaninamide [HPLC Labeling Reagent for e.e. Determination]
A5523	Nalpha-(5-Fluoro-2,4-dinitrophenyl)-L-leucinamide [HPLC Labeling Reagent for e.e. Determination]

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X線結晶構造解析用 / for X-ray Crystallography

C1767	C1683	C1766
C1682

C1767	N-(2-Carboxy-4,5-dichlorobenzoyl)-(+)-10,2-camphorsultam
C1683	N-(2-Carboxy-4,5-dichlorobenzoyl)-(-)-10,2-camphorsultam
C1766	N-(2-Carboxybenzoyl)-(+)-10,2-camphorsultam
C1682	N-(2-Carboxybenzoyl)-(-)-10,2-camphorsultam

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CD励起子キラリティー法 / for Exciton Chirality CD Method

・水酸基用 / for Hydroxyl Groups

A1150	N0025	N0048
B0553	B0558	C0134
C0141	C0445	C1182
D0724	M0721	M0576
N0156	N0176	P0961
P1079	M1338	A0690
B0062	B0105	A0482

A1150	2-Anthracenecarboxylic Acid
N0025	2-Naphthoic Acid
N0048	2-Naphthoyl Chloride
B0553	4-Bromobenzoic Acid
B0558	4-Bromobenzoyl Chloride
C0134	4-Chlorobenzoic Acid
C0141	4-Chlorobenzoyl Chloride
C0445	4-Cyanobenzoic Acid
C1182	4-Cyanobenzoyl Chloride
D0724	4-Dimethylaminobenzoic Acid
M0721	4-Methoxybenzoyl Chloride
M0576	4-Methoxycinnamic Acid
N0156	4-Nitrobenzoic Acid
N0176	4-Nitrobenzoyl Chloride
P0961	4-Phenylbenzoic Acid
P1079	4-Phenylbenzoyl Chloride
M1338	5-(4-Methoxycarbonylphenyl)-10,15,20-triphenylporphyrin
A0690	9-Anthracenecarboxylic Acid
B0062	Benzoic Acid Zone Refined (number of passes:20)
B0105	Benzoyl Chloride
A0482	p-Anisic Acid

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・第一級アミノ基用 / for Primary Amino Groups

N0530	D0645	D1495
D0648

N0530	2,3-Naphthalenedicarboxylic Anhydride
D0645	4-Dimethylaminobenzaldehyde
D1495	4-Dimethylaminobenzaldehyde
D0648	4-Dimethylaminocinnamaldehyde

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・モノアルコール，モノアミン用 / for Monoalcohols, Monoamines

B2124	B3515	A1371
B1185	P1364

B2124	4-[(tert-Butoxycarbonylamino)methyl]pyridine-2-carboxylic Acid [Reagent for application of the exciton chirality method]
B3515	Bis(Zinc Porphyrin) (ca. 5micro mol/L in Dichloromethane) [for CD Spectroscopy]
A1371	N-(tert-Butoxycarbonyl)-1,2-diaminoethane
B1185	N-(tert-Butoxycarbonyl)glycine
P1364	Pentamethylene Bis[4-(10,15,20-triphenylporphin-5-yl)benzoate]dizinc(II) [Reagent for application of the exciton chirality method]

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HPLCカラム，NMR試料管はこちらで紹介しています。

HPLCカラム / HPLC Columns

NMR試料管 / NMR Sample Tube

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文献

1) J. A. Dale, H. S. Mosher, J. Am. Chem. Soc. 1973, 95, 512 [DOI]; I. Ohtani, T. Kusumi, Y. Kashman, H. Kakisawa, J. Am. Chem. Soc. 1991, 113, 4092 [DOI]; N. Harada, M. Watanabe, S. Kuwahara, A. Sugio, Y. Kasai, A. Ichikawa, Tetrahedron : Asymmetry 2000, 11, 1249 [DOI]; 東京化成工業(株), 特開2001-261613.
2) T. Toyo’oka, Biochem. Biophys. Methods 2002, 54, 25 [DOI]; K. Fujii, Y. Ikai, H. Oka, M. Suzuki, K. Harada, Anal. Chem. 1997, 69, 5146 [DOI]; K. Fujii, Y. Ikai, T. Mayumi, H. Oka, M. Suzuki, K. Harada, Anal. Chem. 1997, 69, 3346 [DOI].
3) T. Kurtán, N. Nesnas, F. E. Koehn, Y.-Q. Li, K. Nakanishi, N. Berova, J. Am. Chem. Soc. 2001, 123, 5974 [DOI].
4) T. Ema, D. Tanida, T. Sakai, Org. Lett. 2006, 8, 3773 [DOI]; T. Ema, D. Tanida, T. Sakai, J. Am. Chem. Soc. 2007, 129, 10591 [DOI].

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