不斉合成
Asymmetric Synthesis

　医薬，農薬，あるいは強誘電性液晶を始めとする機能性材料の研究，開発において，光学活性化合物の需要が今まで以上に高まりつつあります。目的とする光学活性化合物を有機合成反応によって得るためには，キラル補助剤，不斉触媒などを用いるジアステレオ区別反応，エナンチオ区別反応が利用されています。そして，より高い光学純度と収率を実現するため，キラル補助剤，不斉触媒の開発が盛んに行われており，多くの成功例が報告されています。例えばカンファーサルタム，オキサゾリジノン誘導体などがキラル補助剤として，BINAP-Rh錯体，オキサザボロリジン誘導体などが優れた不斉触媒として利用され，高い光学純度の生成物が収率良く得られています。
　近年，山田らは，新規な光学活性コバルト(II)錯体触媒MPACを用いるプロキラルケトン，イミンの不斉還元法を開発しました1)。MPACを用いるこの方法は，ケトン，イミンの還元剤として従来から広く利用されている水素化ホウ素ナトリウムを用いて，温和な条件下で高い光学純度の第2級アルコール，アミンを高収率で得ることができます。そのため，有用な光学活性アルコール，アミンの入手法として大変注目されています。

D2239 D2239 C1324 C1324 M1401 M1401
B2048 B2048 B1615 B1615 C1614 C1614
B3296 B3296 D2702 D2702 D2240 D2240
C1325 C1325 M1402 M1402 B1614 B1614
C1615 C1615 C2023 C2023 B3549 B3549
D2686 D2686 D3444 D3444 D3445 D3445
D2176 D2176 A1521 A1521 B2314 B2314
B1844 B1844 D3715 D3715 B2652 B2652
H0862 H0862 T1490 T1490 P1374 P1374
D2128 D2128 B2103 B2103 M1044 M1044
M1070 M1070 T1491 T1491 P1375 P1375
D2129 D2129 B2104 B2104 M1066 M1066
D2175 D2175 B2315 B2315 B2409 B2409
B1845 B1845 D3716 D3716 B2653 B2653
H0863 H0863 B1113 B1113 D3185 D3185
C1326 C1326 B1112 B1112 B2704 B2704
D3186 D3186 C1327 C1327 I0761 I0761
I0762 I0762 M0803 M0803 B1142 B1142
T1499 T1499 T1380 T1380 A1337 A1337
P0794 P0794 B1406 B1406 D3803 D3803
M1170 M1170 D2774 D2774 D2365 D2365
B1528 B1528 B2907 B2907 B2230 B2230
B1143 B1143 P1201 P1201 H0784 H0784
B2165 B2165 I0594 I0594 P1307 P1307
D2729 D2729 A1138 A1138 T2545 T2545
M1169 M1169 I0476 I0476 D2810 D2810
D2801 D2801 B1786 B1786 I0572 I0572
D2130 D2130 D2537 D2537 D2535 D2535
B2034 B2034 B3035 B3035 D2823 D2823
B2217 B2217 B2219 B2219 D2520 D2520
A1548 A1548 B2231 B2231 B1144 B1144
P1241 P1241 X0049 X0049 A0945 A0945
P1294 P1294 H0768 H0768 B2166 B2166
I0573 I0573 P1308 P1308 D2730 D2730
K0028 K0028 B1100 B1100 T1482 T1482
T1381 T1381 A1335 A1335 M1097 M1097
M1183 M1183 P0793 P0793 B1405 B1405
D3804 D3804 M1162 M1162 A1301 A1301
D2775 D2775 D2735 D2735 I0395 I0395
B1529 B1529 B2908 B2908 D3822 D3822
M1161 M1161 I0480 I0480 M1995 M1995
D2811 D2811 D2802 D2802 A2095 A2095
B1754 B1754 I0451 I0451 I0575 I0575
D2131 D2131 P1784 P1784 D2538 D2538
D2536 D2536 I0567 I0567 B2035 B2035
B3036 B3036 B2090 B2090 I0582 I0582
B2218 B2218 B2220 B2220 D2521 D2521
A1699 A1699 D3475 D3475 D3476 D3476
A1534 A1534 A1535 A1535 I0728 I0728
C0347 C0347 C0348 C0348 C0349 C0349
C0350 C0350 C0351 C0351 T0228 T0228
A0177 A0177 P1830 P1830 P0994 P0994
T0539 T0539 V0077 V0077 T1195 T1195
T0003 T0003 T1387 T1387 T0621 T0621
T0230 T0230 A0179 A0179 A1043 A1043
P1404 P1404 P0481 P0481 T0219 T0219
T0541 T0541 V0058 V0058 T1215 T1215
T2637 T2637 B1683 B1683 B1689 B1689
B1684 B1684 B1685 B1685 T2223 T2223
B3398 B3398 P1371 P1371 P1372 P1372
Q0076 Q0076 Q0074 Q0074 Q0006 Q0006
Q0010 Q0010 Q0030 Q0030 T2054 T2054
T1551 T1551 T2055 T2055 T2658 T2658
T2659 T2659 T2660 T2660 T2661 T2661
D2239 (+)-1,4-Di-O-benzyl-D-threitol
C1324 (+)-10,2-Camphorsultam
M1401 (+)-2,2'-Methylenebis[(3aR,8aS)-3a,8a-dihydro-8H-indeno[1,2-d]oxazole]
B2048 (+)-4,5-Bis[hydroxy(diphenyl)methyl]-2,2-dimethyl-1,3-dioxolane
B1615 (+)-4,5-Bis[hydroxy(diphenyl)methyl]-2-methyl-2-phenyl-1,3-dioxolane
C1614 (+)-B-Chlorodiisopinocampheylborane (58% in Hexane, ca. 1.6mol/L)
B3296 (+)-Benzotetramisole
D2702 (+)-Dipivaloyl-D-tartaric Acid
D2240 (-)-1,4-Di-O-benzyl-L-threitol
C1325 (-)-10,2-Camphorsultam
M1402 (-)-2,2'-Methylenebis[(3aS,8aR)-3a,8a-dihydro-8H-indeno[1,2-d]oxazole]
B1614 (-)-4,5-Bis[hydroxy(diphenyl)methyl]-2,2-dimethyl-1,3-dioxolane
C1615 (-)-B-Chlorodiisopinocampheylborane (60% in Hexane, ca. 1.7mol/L)
C2023 (-)-B-Chlorodiisopinocampheylborane (60% in Heptane, ca. 1.7mol/L)
B3549 (-)-Benzotetramisole
D2686 (-)-Dipivaloyl-L-tartaric Acid
D3444 (11R,12R)-9,10-Dihydro-9,10-ethanoanthracene-11,12-diamine
D3445 (11S,12S)-9,10-Dihydro-9,10-ethanoanthracene-11,12-diamine
D2176 (1R,2R)-(+)-1,2-Diphenylethylenediamine
A1521 (1R,2R)-(-)-2-Amino-1-phenyl-1,3-propanediol
B2314 (1R,2R)-N,N'-Bis(2-acetyl-3-oxo-2-butenylidene)-1,2-dimesitylethylenediaminato Cobalt(II)
B1844 (1R,2R)-N,N'-Bis[3-oxo-2-(2,4,6-trimethylbenzoyl)butylidene]-1,2-diphenylethylenediaminato Cobalt(II)
D3715 (1R,2R)-N,N'-Dihydroxy-N,N'-bis(diphenylacetyl)cyclohexane-1,2-diamine
B2652 (1R,2R,4R,5R)-2,5-Bis(3,5-di-tert-butyl-2-hydroxybenzylideneamino)bicyclo[2.2.1]heptane
H0862 (1R,2R,5R)-(+)-2-Hydroxy-3-pinanone
T1490 (1R,2S)-(-)-trans-2-Phenyl-1-cyclohexanol
P1374 (1R,2S)-1-Phenyl-2-(1-pyrrolidinyl)propan-1-ol
D2128 (1R,2S)-2-(Dibutylamino)-1-phenyl-1-propanol
B2103 (1R,2S)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenyl-1-propanol
M1044 (1R,2S,5R)-(-)-Menthyl (S)-p-Toluenesulfinate
M1070 (1S)-(-)-10-Mercaptoisoborneol
T1491 (1S,2R)-(+)-trans-2-Phenyl-1-cyclohexanol
P1375 (1S,2R)-1-Phenyl-2-(1-pyrrolidinyl)propan-1-ol
D2129 (1S,2R)-2-(Dibutylamino)-1-phenyl-1-propanol
B2104 (1S,2R)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenyl-1-propanol
M1066 (1S,2R,5S)-(+)-Menthyl (R)-p-Toluenesulfinate
D2175 (1S,2S)-(-)-1,2-Diphenylethylenediamine
B2315 (1S,2S)-N,N'-Bis(2-acetyl-3-oxo-2-butenylidene)-1,2-dimesitylethylenediaminato Cobalt(II)
B2409 (1S,2S)-N,N'-Bis[(R)-2-hydroxy-2'-phenyl-1,1'-binaphthyl-3-ylmethylene]-1,2-diphenylethylenediaminato Manganese(III) Acetate
B1845 (1S,2S)-N,N'-Bis[3-oxo-2-(2,4,6-trimethylbenzoyl)butylidene]-1,2-diphenylethylenediaminato Cobalt(II)
D3716 (1S,2S)-N,N'-Dihydroxy-N,N'-bis(diphenylacetyl)cyclohexane-1,2-diamine
B2653 (1S,2S,4S,5S)-2,5-Bis(3,5-di-tert-butyl-2-hydroxybenzylideneamino)bicyclo[2.2.1]heptane
H0863 (1S,2S,5S)-(-)-2-Hydroxy-3-pinanone
B1113 (2R,3R)-(-)-1,4-Bis(diphenylphosphino)-2,3-O-isopropylidene-2,3-butanediol
D3185 (2R,5R)-2,5-Diphenylpyrrolidine
C1326 (2R,8aS)-(+)-(Camphorylsulfonyl)oxaziridine [Asymmetric Oxidizing Reagent]
B1112 (2S,3S)-(+)-1,4-Bis(diphenylphosphino)-2,3-O-isopropylidene-2,3-butanediol
B2704 (2S,3S)-(-)-Bis(diphenylphosphino)butane
D3186 (2S,5S)-2,5-Diphenylpyrrolidine
C1327 (2S,8aR)-(-)-(Camphorylsulfonyl)oxaziridine [Asymmetric Oxidizing Reagent]
I0761 (4R)-(+)-4-Isopropyl-5,5-diphenyl-2-oxazolidinone
I0762 (4S)-(-)-4-Isopropyl-5,5-diphenyl-2-oxazolidinone
M0803 (4S,5S)-(-)-4-Methoxymethyl-2-methyl-5-phenyl-2-oxazoline
B1142 (R)-(+)-1,1'-Bi-2-naphthol
T1499 (R)-(+)-1,1,2-Triphenyl-1,2-ethanediol
T1380 (R)-(+)-1-(p-Tolyl)ethylamine
A1337 (R)-(+)-1-Amino-2-(methoxymethyl)pyrrolidine
P0794 (R)-(+)-1-Phenylethylamine
B1406 (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl
D3803 (R)-(+)-2-(Diphenylmethyl)pyrrolidine
M1170 (R)-(+)-2-(Methoxymethyl)-1-pyrrolidinecarboxaldehyde
D2774 (R)-(+)-2-Diphenylphosphino-2'-methoxy-1,1'-binaphthyl
D2365 (R)-(+)-alpha,alpha-Diphenyl-2-pyrrolidinemethanol
B1528 (R)-(+)-N-Benzyl-1-phenylethylamine
B2907 (R)-(+)-tert-Butylsulfinamide
B2230 (R)-(-)-1,1'-Binaphthyl-2,2'-diyl Bis(trifluoromethanesulfonate)
B1143 (R)-(-)-1,1'-Binaphthyl-2,2'-diyl Hydrogen Phosphate
P1201 (R)-(-)-2-Phenylglycinol
H0784 (R)-(-)-2-[Hydroxy(diphenyl)methyl]-1-methylpyrrolidine
B2165 (R)-(-)-4-Benzyl-3-propionyl-2-oxazolidinone
I0594 (R)-(-)-4-Isopropyl-3-propionyl-2-oxazolidinone
P1307 (R)-(-)-4-Phenyl-2-oxazolidinone
D2729 (R)-(-)-6,6'-Dibromo-1,1'-bi-2-naphthol (contains 5% Dichloromethane at maximum)
A1138 (R)-(-)-Acetylcarbonyl(eta5-2,4-cyclopentadien-1-yl)(triphenylphosphine)iron
T2545 (R)-(p-Toluenesulfinyl)ferrocene
M1169 (R)-2-(Methoxymethyl)pyrrolidine
I0476 (R)-2-Isopropylamino-2-phenylethanol
D2810 (R)-3,3'-Dibromo-1,1'-bi-2-naphthol
D2801 (R)-3,3'-Dibromo-2,2'-dimethoxy-1,1'-binaphthyl
B1786 (R)-4-Benzyl-2-oxazolidinone
I0572 (R)-4-Isopropyl-2-oxazolidinone
D2130 (R)-5,5-Diphenyl-2-methyl-3,4-propano-1,3,2-oxazaborolidine
D2537 (R)-N,N-Dimethyl-1-[(S)-1',2-bis(diphenylphosphino)ferrocenyl]ethylamine
D2535 (R)-N,N-Dimethyl-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine
B2034 (R,R)-(+)-Bis(alpha-methylbenzyl)amine Hydrochloride
B3035 (R,R)-1,2-Bis[(2-methoxyphenyl)phenylphosphino]ethane
D2823 (R,R)-2,2'-Isopropylidenebis(4-phenyl-2-oxazoline)
B2217 (R,R)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridine
B2219 (R,R)-2,6-Bis(4-phenyl-2-oxazolin-2-yl)pyridine
D2520 (R,R)-N,N'-Bis(trifluoromethanesulfonyl)-1,2-diphenylethylenediamine
A1548 (R,R)-N-(2-Amino-1,2-diphenylethyl)-p-toluenesulfonamide
B2231 (S)-(+)-1,1'-Binaphthyl-2,2'-diyl Bis(trifluoromethanesulfonate)
B1144 (S)-(+)-1,1'-Binaphthyl-2,2'-diyl Hydrogen Phosphate
P1241 (S)-(+)-1-(2-Pyrrolidinylmethyl)pyrrolidine
X0049 (S)-(+)-2-(2,6-Xylidinomethyl)pyrrolidine
A0945 (S)-(+)-2-(Anilinomethyl)pyrrolidine
P1294 (S)-(+)-2-Phenylglycinol
H0768 (S)-(+)-2-[Hydroxy(diphenyl)methyl]-1-methylpyrrolidine
B2166 (S)-(+)-4-Benzyl-3-propionyl-2-oxazolidinone
I0573 (S)-(+)-4-Isopropyl-3-propionyl-2-oxazolidinone
P1308 (S)-(+)-4-Phenyl-2-oxazolidinone
D2730 (S)-(+)-6,6'-Dibromo-1,1'-bi-2-naphthol (contains 5% Dichloromethane at maximum)
K0028 (S)-(+)-Ketopinic Acid
B1100 (S)-(-)-1,1'-Bi-2-naphthol
T1482 (S)-(-)-1,1,2-Triphenyl-1,2-ethanediol
T1381 (S)-(-)-1-(p-Tolyl)ethylamine
A1335 (S)-(-)-1-Amino-2-(methoxymethyl)pyrrolidine
M1097 (S)-(-)-1-Methyl-2-(1-naphthylaminomethyl)pyrrolidine
M1183 (S)-(-)-1-Methyl-2-(1-piperidinomethyl)pyrrolidine
P0793 (S)-(-)-1-Phenylethylamine
B1405 (S)-(-)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl
D3804 (S)-(-)-2-(Diphenylmethyl)pyrrolidine
M1162 (S)-(-)-2-(Methoxymethyl)-1-pyrrolidinecarboxaldehyde
A1301 (S)-(-)-2-Aminomethyl-1-ethylpyrrolidine
D2775 (S)-(-)-2-Diphenylphosphino-2'-methoxy-1,1'-binaphthyl
D2735 (S)-(-)-alpha,alpha-Diphenyl-2-pyrrolidinemethanol
I0395 (S)-(-)-Indoline-2-carboxylic Acid
B1529 (S)-(-)-N-Benzyl-1-phenylethylamine
B2908 (S)-(-)-tert-Butylsulfinamide
D3822 (S)-1-(Diphenylphosphino)-2-[(S)-4-isopropyloxazolin-2-yl]ferrocene
M1161 (S)-2-(Methoxymethyl)pyrrolidine
I0480 (S)-2-Isopropylamino-3-methyl-1-butanol
M1995 (S)-2-[(1-Methyl-2-pyrrolidinyl)methyl]isoindoline Dihydrochloride
D2811 (S)-3,3'-Dibromo-1,1'-bi-2-naphthol
D2802 (S)-3,3'-Dibromo-2,2'-dimethoxy-1,1'-binaphthyl
A2095 (S)-4-(4-Aminobenzyl)-2-oxazolidinone
B1754 (S)-4-Benzyl-2-oxazolidinone
I0451 (S)-4-Isopropyl-2-oxazolidinone
I0575 (S)-4-Isopropylthiazolidine-2-thione
D2131 (S)-5,5-Diphenyl-2-methyl-3,4-propano-1,3,2-oxazaborolidine
P1784 (S)-5-(Pyrrolidin-2-yl)-1H-tetrazole
D2538 (S)-N,N-Dimethyl-1-[(R)-1',2-bis(diphenylphosphino)ferrocenyl]ethylamine
D2536 (S)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine
I0567 (S,S)-(-)-2,2'-Isopropylidenebis(4-tert-butyl-2-oxazoline)
B2035 (S,S)-(-)-Bis(alpha-methylbenzyl)amine Hydrochloride
B3036 (S,S)-1,2-Bis[(2-methoxyphenyl)phenylphosphino]ethane
B2090 (S,S)-1,2-Bis[(tert-butyl)methylphosphino]ethane[eta-(2,5-norbornadiene)]rhodium(I) Tetrafluoroborate
I0582 (S,S)-2,2'-Isopropylidenebis(4-phenyl-2-oxazoline)
B2218 (S,S)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridine
B2220 (S,S)-2,6-Bis(4-phenyl-2-oxazolin-2-yl)pyridine
D2521 (S,S)-N,N'-Bis(trifluoromethanesulfonyl)-1,2-diphenylethylenediamine
A1699 (S,S)-N-(2-Amino-1,2-diphenylethyl)-p-toluenesulfonamide
D3475 6,10-Dibenzyl-N,N'-dimethyl-N,N,N',N'-tetrakis(4-methylbenzyl)-1,4-dioxaspiro[4.5]decane-(2R,3R)-diylbis(methylammonium) Tetrafluoroborate [=(R,R)-TaDiAS-2nd]
D3476 6,10-Dibenzyl-N,N'-dimethyl-N,N,N',N'-tetrakis(4-methylbenzyl)-1,4-dioxaspiro[4.5]decane-(2S,3S)-diylbis(methylammonium) Tetrafluoroborate [=(S,S)-TaDiAS-2nd]
A1534 Acetic Acid (1R,2S)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenylpropyl Ester [Reagent for double aldol reaction]
A1535 Acetic Acid (1S,2R)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenylpropyl Ester [Reagent for double aldol reaction]
I0728 beta-Isocupreidine
C0347 Cinchonidine
C0348 Cinchonidine Dihydrochloride
C0349 Cinchonidine Sulfate
C0350 Cinchonine
C0351 Cinchonine Hydrochloride Hydrate
T0228 D-(+)-Threonine
A0177 D-Alanine
P1830 D-Pipecolic Acid
P0994 D-Proline
T0539 D-Tryptophan
V0077 D-Valinol
T1195 Diethyl D-(-)-Tartrate
T0003 Diethyl L-(+)-Tartrate
T1387 Diisopropyl D-(-)-Tartrate
T0621 Diisopropyl L-(+)-Tartrate
T0230 L-(-)-Threonine
A0179 L-Alanine
A1043 L-Azetidine-2-carboxylic Acid [Antagonist of L-Proline]
P1404 L-Pipecolic Acid
P0481 L-Proline
T0219 L-Thioproline
T0541 L-Tryptophan
V0058 L-Valinol
T1215 Levamisole Hydrochloride
T2637 N-(2-Thiophenesulfonyl)-L-prolinamide Trifluoroacetate
B1683 N-Benzylcinchonidinium Chloride [Chiral Phase-Transfer Catalyst]
B1689 N-Benzylcinchoninium Chloride [Chiral Phase-Transfer Catalyst]
B1684 N-Benzylquinidinium Chloride [Chiral Phase-Transfer Catalyst]
B1685 N-Benzylquininium Chloride [Chiral Phase-Transfer Catalyst]
T2223 Nalpha-(2,4,6-Triisopropylbenzenesulfonyl)-O-(tert-butyldiphenylsilyl)-pros-methyl-L-histidinol
B3398 O-tert-Butyl-L-threonine
P1371 Propionic Acid (1R,2S)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenylpropyl Ester [Reagent for anti-selective asymmetric aldol reaction]
P1372 Propionic Acid (1S,2R)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenylpropyl Ester [Reagent for anti-selective asymmetric aldol reaction]
Q0076 Quincoridine
Q0074 Quincorine
Q0006 Quinidine
Q0010 Quinidine Sulfate Dihydrate
Q0030 Quinine Hydrochloride Dihydrate
T2054 Tetrakis[N-phthaloyl-(R)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct
T1551 Tetrakis[N-phthaloyl-(S)-phenylalaninato]dirhodium Ethyl Acetate Adduct
T2055 Tetrakis[N-phthaloyl-(S)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct
T2658 Tetrakis[N-tetrachlorophthaloyl-(R)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct
T2659 Tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct
T2660 Tetrakis[N-tetrafluorophthaloyl-(R)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct
T2661 Tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct
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文献

1) 山田 徹, 永田卓司, 大塚雄紀, 池野健人, 向山光昭, 有機合成化学協会誌, 2003, 61, 843; T. Yamada, T. Nagata, K. D. Sugi, K. Yorozu, T. Ikeno, Y. Ohtsuka, D. Miyazaki, T. Mukaiyama, Chem. Eur. J., 2003, 9, 4485 [DOI]; 山田 徹, ファインケミカル, 2010, 39(1), 13.

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