Asymmetric Synthesis

In the research and development of pharmaceuticals, agricultural chemicals or functional materials starting with ferroelectrical liquid crystals, the demand for optically active compounds has increased more than ever. In order to obtain the desired optically active compounds through synthesis, diastereo-differentiating and enantio-differentiating reactions have employed chiral auxiliaries or asymmetric catalysts. In order to achieve even higher optical purity and yield, new chiral auxiliaries and asymmetric catalysts are being developed and a considerable number of successful results have been reported. For instance, camphorsultam and oxazolidinone derivatives are utilized as chiral auxiliaries. BINAP-Rh complexes and oxazaborolidine derivatives are excellent asymmetric catalysts. All of these new developments produce products of high optical purity and good reaction yields.
Recently, Yamada and co-workers have developed a pro-chiral ketone and imine asymmetric reduction which uses the newly developed optically active cobalt(II) complex catalyst MPAC.1) Through this asymmetric reduction using MPAC, secondary alcohols and amines of high optical purity can be obtained in good yields. The reaction proceeds under relatively moderate temperatures and utilize sodium borohydride, which has been traditionally employed as a reducing agent of ketones and imines. For this reason, this method is receiving much attention as a route to useful optically active alcohols and amines.

A1534 A1534 A1535 A1535 A0177 A0177
A0179 A0179 D2365 D2365 D2735 D2735
A2095 A2095 A1548 A1548 A1699 A1699
A2316 A2316 A2317 A2317 A1335 A1335
A1337 A1337 A1301 A1301 A0945 A0945
A1043 A1043 B3296 B3296 B3549 B3549
B1683 B1683 B1689 B1689 B2103 B2103
B2104 B2104 P1371 P1371 P1372 P1372
B1754 B1754 B1786 B1786 B1528 B1528
B1529 B1529 B2165 B2165 B2166 B2166
B1684 B1684 B1685 B1685 B1100 B1100
B1142 B1142 B2230 B2230 B2231 B2231
B1143 B1143 B1144 B1144 B2314 B2314
B2315 B2315 B2090 B2090 B2652 B2652
B2653 B2653 B3449 B3449 B3450 B3450
B1405 B1405 B1406 B1406 B2704 B2704
B1112 B1112 B1113 B1113 B1614 B1614
B2048 B2048 B1615 B1615 B2409 B2409
B2217 B2217 B2218 B2218 B3035 B3035
B3036 B3036 B2034 B2034 B2035 B2035
B1844 B1844 B1845 B1845 B2219 B2219
B2220 B2220 D2520 D2520 D2521 D2521
B2907 B2907 B2908 B2908 B3398 B3398
C1324 C1324 C1325 C1325 C1326 C1326
C1327 C1327 C1614 C1614 C1615 C1615
C2023 C2023 C0347 C0347 C0348 C0348
C0349 C0349 C0350 C0350 C0351 C0351
D3475 D3475 D3476 D3476 D2239 D2239
D2240 D2240 D2729 D2729 D2730 D2730
D2810 D2810 D2811 D2811 D2801 D2801
D2802 D2802 D2128 D2128 D2129 D2129
T1195 T1195 T0003 T0003 D3444 D3444
D3445 D3445 D3715 D3715 D3716 D3716
T1387 T1387 T0621 T0621 D3808 D3808
D3809 D3809 D2537 D2537 D2538 D2538
D2535 D2535 D2536 D2536 D2175 D2175
D2176 D2176 D2130 D2130 D2131 D2131
D3803 D3803 D3804 D3804 D3822 D3822
D3185 D3185 D3186 D3186 D2686 D2686
D2702 D2702 H0768 H0768 H0784 H0784
H0862 H0862 H0863 H0863 H1322 H1322
I0395 I0395 I0728 I0728 I0480 I0480
I0476 I0476 I0761 I0761 I0762 I0762
I0567 I0567 I0795 I0795 D2823 D2823
I0582 I0582 I0451 I0451 I0572 I0572
I0573 I0573 I0594 I0594 I0575 I0575
K0028 K0028 T1215 T1215 M1044 M1044
M1066 M1066 M1070 M1070 M0803 M0803
M1161 M1161 M1169 M1169 M1162 M1162
M1170 M1170 M1401 M1401 M1402 M1402
M1097 M1097 M1183 M1183 M1995 M1995
T1490 T1490 T1491 T1491 P0793 P0793
P0794 P0794 P1201 P1201 P1294 P1294
P1307 P1307 P1308 P1308 P1374 P1374
P1375 P1375 P1404 P1404 P1830 P1830
P0481 P0481 P0994 P0994 T2545 T2545
T1380 T1380 T1381 T1381 P1241 P1241
P1925 P1925 P1784 P1784 Q0076 Q0076
Q0074 Q0074 Q0006 Q0006 Q0010 Q0010
Q0030 Q0030 P1947 P1947 T2054 T2054
T2055 T2055 T1551 T1551 T2658 T2658
T2659 T2659 T2660 T2660 T2661 T2661
T2637 T2637 T0219 T0219 T0228 T0228
T0230 T0230 T2223 T2223 T2578 T2578
T2579 T2579 T1482 T1482 T1499 T1499
T0539 T0539 T0541 T0541 V0058 V0058
V0077 V0077
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]
A0177 D-Alanine
A0179 L-Alanine
D2365 (R)-(+)-alpha,alpha-Diphenyl-2-pyrrolidinemethanol
D2735 (S)-(-)-alpha,alpha-Diphenyl-2-pyrrolidinemethanol
A2095 (S)-4-(4-Aminobenzyl)-2-oxazolidinone
A1548 (R,R)-N-(2-Amino-1,2-diphenylethyl)-p-toluenesulfonamide
A1699 (S,S)-N-(2-Amino-1,2-diphenylethyl)-p-toluenesulfonamide
A2316 (R)-(+)-2-Amino-2'-hydroxy-1,1'-binaphthyl
A2317 (S)-(-)-2-Amino-2'-hydroxy-1,1'-binaphthyl
A1335 (S)-(-)-1-Amino-2-(methoxymethyl)pyrrolidine
A1337 (R)-(+)-1-Amino-2-(methoxymethyl)pyrrolidine
A1301 (S)-(-)-2-Aminomethyl-1-ethylpyrrolidine
A0945 (S)-(+)-2-(Anilinomethyl)pyrrolidine
A1043 L-Azetidine-2-carboxylic Acid [Antagonist of L-Proline]
B3296 (+)-Benzotetramisole
B3549 (-)-Benzotetramisole
B1683 N-Benzylcinchonidinium Chloride [Chiral Phase-Transfer Catalyst]
B1689 N-Benzylcinchoninium Chloride [Chiral Phase-Transfer Catalyst]
B2103 (1R,2S)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenyl-1-propanol
B2104 (1S,2R)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenyl-1-propanol
P1371 (1R,2S)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenylpropyl Propionate [Reagent for anti-selective asymmetric aldol reaction]
P1372 (1S,2R)-2-[N-Benzyl-N-(mesitylenesulfonyl)amino]-1-phenylpropyl Propionate [Reagent for anti-selective asymmetric aldol reaction]
B1754 (S)-4-Benzyl-2-oxazolidinone
B1786 (R)-4-Benzyl-2-oxazolidinone
B1528 (R)-(+)-N-Benzyl-1-phenylethylamine
B1529 (S)-(-)-N-Benzyl-1-phenylethylamine
B2165 (R)-(-)-4-Benzyl-3-propionyl-2-oxazolidinone
B2166 (S)-(+)-4-Benzyl-3-propionyl-2-oxazolidinone
B1684 N-Benzylquinidinium Chloride [Chiral Phase-Transfer Catalyst]
B1685 N-Benzylquininium Chloride [Chiral Phase-Transfer Catalyst]
B1100 (S)-(-)-1,1'-Bi-2-naphthol
B1142 (R)-(+)-1,1'-Bi-2-naphthol
B2230 (R)-(-)-1,1'-Binaphthyl-2,2'-diyl Bis(trifluoromethanesulfonate)
B2231 (S)-(+)-1,1'-Binaphthyl-2,2'-diyl Bis(trifluoromethanesulfonate)
B1143 (R)-(-)-1,1'-Binaphthyl-2,2'-diyl Hydrogen Phosphate
B1144 (S)-(+)-1,1'-Binaphthyl-2,2'-diyl Hydrogen Phosphate
B2314 (1R,2R)-N,N'-Bis(2-acetyl-3-oxo-2-butenylidene)-1,2-dimesitylethylenediaminato Cobalt(II)
B2315 (1S,2S)-N,N'-Bis(2-acetyl-3-oxo-2-butenylidene)-1,2-dimesitylethylenediaminato Cobalt(II)
B2090 (S,S)-1,2-Bis[(tert-butyl)methylphosphino]ethane[eta-(2,5-norbornadiene)]rhodium(I) Tetrafluoroborate
B2652 (1R,2R,4R,5R)-2,5-Bis(3,5-di-tert-butyl-2-hydroxybenzylideneamino)bicyclo[2.2.1]heptane
B2653 (1S,2S,4S,5S)-2,5-Bis(3,5-di-tert-butyl-2-hydroxybenzylideneamino)bicyclo[2.2.1]heptane
B3449 (2R,3R)-(-)-2,3-Bis(diphenylphosphino)bicyclo[2.2.1]hept-5-ene
B3450 (2S,3S)-(+)-2,3-Bis(diphenylphosphino)bicyclo[2.2.1]hept-5-ene
B1405 (S)-(-)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl
B1406 (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl
B2704 (2S,3S)-(-)-Bis(diphenylphosphino)butane
B1112 (2S,3S)-(+)-1,4-Bis(diphenylphosphino)-2,3-O-isopropylidene-2,3-butanediol
B1113 (2R,3R)-(-)-1,4-Bis(diphenylphosphino)-2,3-O-isopropylidene-2,3-butanediol
B1614 (-)-4,5-Bis[hydroxy(diphenyl)methyl]-2,2-dimethyl-1,3-dioxolane
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
B2409 (1S,2S)-N,N'-Bis[(R)-2-hydroxy-2'-phenyl-1,1'-binaphthyl-3-ylmethylene]-1,2-diphenylethylenediaminato Manganese(III) Acetate
B2217 (R,R)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridine
B2218 (S,S)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridine
B3035 (R,R)-1,2-Bis[(2-methoxyphenyl)phenylphosphino]ethane
B3036 (S,S)-1,2-Bis[(2-methoxyphenyl)phenylphosphino]ethane
B2034 (R,R)-(+)-Bis(alpha-methylbenzyl)amine Hydrochloride
B2035 (S,S)-(-)-Bis(alpha-methylbenzyl)amine Hydrochloride
B1844 (1R,2R)-N,N'-Bis[3-oxo-2-(2,4,6-trimethylbenzoyl)butylidene]-1,2-diphenylethylenediaminato Cobalt(II)
B1845 (1S,2S)-N,N'-Bis[3-oxo-2-(2,4,6-trimethylbenzoyl)butylidene]-1,2-diphenylethylenediaminato Cobalt(II)
B2219 (R,R)-2,6-Bis(4-phenyl-2-oxazolin-2-yl)pyridine
B2220 (S,S)-2,6-Bis(4-phenyl-2-oxazolin-2-yl)pyridine
D2520 (R,R)-N,N'-Bis(trifluoromethanesulfonyl)-1,2-diphenylethylenediamine
D2521 (S,S)-N,N'-Bis(trifluoromethanesulfonyl)-1,2-diphenylethylenediamine
B2907 (R)-(+)-tert-Butylsulfinamide
B2908 (S)-(-)-tert-Butylsulfinamide
B3398 O-tert-Butyl-L-threonine
C1324 (+)-10,2-Camphorsultam
C1325 (-)-10,2-Camphorsultam
C1326 (2R,8aS)-(+)-(Camphorylsulfonyl)oxaziridine [Asymmetric Oxidizing Reagent]
C1327 (2S,8aR)-(-)-(Camphorylsulfonyl)oxaziridine [Asymmetric Oxidizing Reagent]
C1614 (+)-B-Chlorodiisopinocampheylborane (58% in Hexane, ca. 1.6mol/L)
C1615 (-)-B-Chlorodiisopinocampheylborane (60% in Hexane, ca. 1.7mol/L)
C2023 (-)-B-Chlorodiisopinocampheylborane (60% in Heptane, ca. 1.7mol/L)
C0347 Cinchonidine
C0348 Cinchonidine Dihydrochloride
C0349 Cinchonidine Sulfate Dihydrate
C0350 Cinchonine
C0351 Cinchonine Hydrochloride Hydrate
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]
D2239 (+)-1,4-Di-O-benzyl-D-threitol
D2240 (-)-1,4-Di-O-benzyl-L-threitol
D2729 (R)-(-)-6,6'-Dibromo-1,1'-bi-2-naphthol
D2730 (S)-(+)-6,6'-Dibromo-1,1'-bi-2-naphthol
D2810 (R)-3,3'-Dibromo-1,1'-bi-2-naphthol
D2811 (S)-3,3'-Dibromo-1,1'-bi-2-naphthol
D2801 (R)-3,3'-Dibromo-2,2'-dimethoxy-1,1'-binaphthyl
D2802 (S)-3,3'-Dibromo-2,2'-dimethoxy-1,1'-binaphthyl
D2128 (1R,2S)-2-(Dibutylamino)-1-phenyl-1-propanol
D2129 (1S,2R)-2-(Dibutylamino)-1-phenyl-1-propanol
T1195 Diethyl D-(-)-Tartrate
T0003 Diethyl L-(+)-Tartrate
D3444 (11R,12R)-9,10-Dihydro-9,10-ethanoanthracene-11,12-diamine
D3445 (11S,12S)-9,10-Dihydro-9,10-ethanoanthracene-11,12-diamine
D3715 (1R,2R)-N,N'-Dihydroxy-N,N'-bis(diphenylacetyl)cyclohexane-1,2-diamine
D3716 (1S,2S)-N,N'-Dihydroxy-N,N'-bis(diphenylacetyl)cyclohexane-1,2-diamine
T1387 Diisopropyl D-(-)-Tartrate
T0621 Diisopropyl L-(+)-Tartrate
D3808 (1R,2R)-N,N'-Dimethyl-N,N'-bis(3,3-dimethylbutyl)cyclohexane-1,2-diamine
D3809 (1S,2S)-N,N'-Dimethyl-N,N'-bis(3,3-dimethylbutyl)cyclohexane-1,2-diamine
D2537 (R)-N,N-Dimethyl-1-[(S)-1',2-bis(diphenylphosphino)ferrocenyl]ethylamine
D2538 (S)-N,N-Dimethyl-1-[(R)-1',2-bis(diphenylphosphino)ferrocenyl]ethylamine
D2535 (R)-N,N-Dimethyl-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethylamine
D2536 (S)-N,N-Dimethyl-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine
D2175 (1S,2S)-(-)-1,2-Diphenylethylenediamine
D2176 (1R,2R)-(+)-1,2-Diphenylethylenediamine
D2130 (R)-5,5-Diphenyl-2-methyl-3,4-propano-1,3,2-oxazaborolidine
D2131 (S)-5,5-Diphenyl-2-methyl-3,4-propano-1,3,2-oxazaborolidine
D3803 (R)-(+)-2-(Diphenylmethyl)pyrrolidine
D3804 (S)-(-)-2-(Diphenylmethyl)pyrrolidine
D3822 (S)-1-(Diphenylphosphino)-2-[(S)-4-isopropyloxazolin-2-yl]ferrocene
D3185 (2R,5R)-2,5-Diphenylpyrrolidine
D3186 (2S,5S)-2,5-Diphenylpyrrolidine
D2686 (-)-Dipivaloyl-L-tartaric Acid
D2702 (+)-Dipivaloyl-D-tartaric Acid
H0768 (S)-(+)-2-[Hydroxy(diphenyl)methyl]-1-methylpyrrolidine
H0784 (R)-(-)-2-[Hydroxy(diphenyl)methyl]-1-methylpyrrolidine
H0862 (1R,2R,5R)-(+)-2-Hydroxy-3-pinanone
H0863 (1S,2S,5S)-(-)-2-Hydroxy-3-pinanone
H1322 1-Hydroxytetraphenylcylclopentadienyl(tetraphenyl-2,4-cyclopentadien-1-one)-mu-hydrotetracarbonyldiruthenium(II)
I0395 (S)-(-)-Indoline-2-carboxylic Acid
I0728 beta-Isocupreidine
I0480 (S)-2-Isopropylamino-3-methyl-1-butanol
I0476 (R)-2-Isopropylamino-2-phenylethanol
I0761 (4R)-(+)-4-Isopropyl-5,5-diphenyl-2-oxazolidinone
I0762 (4S)-(-)-4-Isopropyl-5,5-diphenyl-2-oxazolidinone
I0567 (S,S)-(-)-2,2'-Isopropylidenebis(4-tert-butyl-2-oxazoline)
I0795 (R,R)-(+)-2,2'-Isopropylidenebis(4-tert-butyl-2-oxazoline)
D2823 (R,R)-2,2'-Isopropylidenebis(4-phenyl-2-oxazoline)
I0582 (S,S)-2,2'-Isopropylidenebis(4-phenyl-2-oxazoline)
I0451 (S)-4-Isopropyl-2-oxazolidinone
I0572 (R)-4-Isopropyl-2-oxazolidinone
I0573 (S)-(+)-4-Isopropyl-3-propionyl-2-oxazolidinone
I0594 (R)-(-)-4-Isopropyl-3-propionyl-2-oxazolidinone
I0575 (S)-4-Isopropylthiazolidine-2-thione
K0028 (S)-(+)-Ketopinic Acid
T1215 Levamisole Hydrochloride
M1044 (1R,2S,5R)-(-)-Menthyl (S)-p-Toluenesulfinate
M1066 (1S,2R,5S)-(+)-Menthyl (R)-p-Toluenesulfinate
M1070 (1S)-(-)-10-Mercaptoisoborneol
M0803 (4S,5S)-(-)-4-Methoxymethyl-2-methyl-5-phenyl-2-oxazoline
M1161 (S)-2-(Methoxymethyl)pyrrolidine
M1169 (R)-2-(Methoxymethyl)pyrrolidine
M1162 (S)-(-)-2-(Methoxymethyl)-1-pyrrolidinecarboxaldehyde
M1170 (R)-(+)-2-(Methoxymethyl)-1-pyrrolidinecarboxaldehyde
M1401 (+)-2,2'-Methylenebis[(3aR,8aS)-3a,8a-dihydro-8H-indeno[1,2-d]oxazole]
M1402 (-)-2,2'-Methylenebis[(3aS,8aR)-3a,8a-dihydro-8H-indeno[1,2-d]oxazole]
M1097 (S)-(-)-1-Methyl-2-(1-naphthylaminomethyl)pyrrolidine
M1183 (S)-(-)-1-Methyl-2-(1-piperidinomethyl)pyrrolidine
M1995 (S)-2-[(1-Methyl-2-pyrrolidinyl)methyl]isoindoline Dihydrochloride
T1490 (1R,2S)-(-)-trans-2-Phenyl-1-cyclohexanol
T1491 (1S,2R)-(+)-trans-2-Phenyl-1-cyclohexanol
P0793 (S)-(-)-1-Phenylethylamine
P0794 (R)-(+)-1-Phenylethylamine
P1201 (R)-(-)-2-Phenylglycinol
P1294 (S)-(+)-2-Phenylglycinol
P1307 (R)-(-)-4-Phenyl-2-oxazolidinone
P1308 (S)-(+)-4-Phenyl-2-oxazolidinone
P1374 (1R,2S)-1-Phenyl-2-(1-pyrrolidinyl)propan-1-ol
P1375 (1S,2R)-1-Phenyl-2-(1-pyrrolidinyl)propan-1-ol
P1404 L-Pipecolic Acid
P1830 D-Pipecolic Acid
P0481 L-Proline
P0994 D-Proline
T2545 (R)-(p-Toluenesulfinyl)ferrocene
T1380 (R)-(+)-1-(p-Tolyl)ethylamine
T1381 (S)-(-)-1-(p-Tolyl)ethylamine
P1241 (S)-(+)-1-(2-Pyrrolidinylmethyl)pyrrolidine
P1925 (R)-(-)-1-(2-Pyrrolidinylmethyl)pyrrolidine
P1784 (S)-5-(Pyrrolidin-2-yl)-1H-tetrazole
Q0076 Quincoridine
Q0074 Quincorine
Q0006 Quinidine
Q0010 Quinidine Sulfate Dihydrate
Q0030 Quinine Hydrochloride Dihydrate
P1947 (4S,4'S)-2,2'-(Pentane-3,3'-diyl)bis(4-benzyl-4,5-dihydrooxazole)
T2054 Tetrakis[N-phthaloyl-(R)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct
T2055 Tetrakis[N-phthaloyl-(S)-tert-leucinato]dirhodium Bis(ethyl Acetate) Adduct
T1551 Tetrakis[N-phthaloyl-(S)-phenylalaninato]dirhodium 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
T2637 N-(2-Thiophenesulfonyl)-L-prolinamide Trifluoroacetate
T0219 L-Thioproline
T0228 D-(+)-Threonine
T0230 L-(-)-Threonine
T2223 Nalpha-(2,4,6-Triisopropylbenzenesulfonyl)-O-(tert-butyldiphenylsilyl)-pros-methyl-L-histidinol
T2578 (1R,4R,5R)-4,7,7-Trimethyl-6-thiabicyclo[3.2.1]octane
T2579 (1S,4S,5S)-4,7,7-Trimethyl-6-thiabicyclo[3.2.1]octane
T1482 (S)-(-)-1,1,2-Triphenyl-1,2-ethanediol
T1499 (R)-(+)-1,1,2-Triphenyl-1,2-ethanediol
T0539 D-Tryptophan
T0541 L-Tryptophan
V0058 L-Valinol
V0077 D-Valinol

Literature

1) T. Yamada, T. Nagata, Y. Ohtsuka, T. Ikeno, T. Mukaiyama, Yuki Gosei Kagaku Kyokaishi (J. Synth. Org. Chem., Jpn.), 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].


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