2549-14-6

Basic information

• Product Name: (R)-(+)-2-Phenylglycinol
• Synonyms: RARECHEM AL BW 2319;(R)-(-)-2-AMINO-1-PHENYLETHANOL;(R)-2-AMINO-1-PHENYLETHANOL;(R)-1-PHENYL-1-HYDROXY-2-AMINOETHANE;(R)-ALPHA-(AMINOMETHYL)BENZYL ALCOHOL;BENZENEMETHANOL, A-(AMINOMETHYL)-, (AR)-;(r)-(-)-à-(aminomethyl)benzyl alcohol;(r)-α-(aminomethyl)benzyl alcohol
• CAS NO: 2549-14-6
• Molecular Formula: C₈H₁₁NO
• Molecular Weight: 137.18
• EINECS: 1308068-626-2
• Product Categories: pharmacetical;Benzene series;Amino Acid Derivatives
• Mol File: 2549-14-6.mol
• Article Data: 43

Chemical Properties

• Melting Point: 59-65 °C(lit.)
• Boiling Point: 160°C/17mm
• Flash Point: >230 °F
• Appearance: /
• Density: 1.104 g/cm³
• Vapor Pressure: 0.00148mmHg at 25°C
• Refractive Index: 1.572
• PKA: 12.04±0.35(Predicted)
• Sensitive: Air Sensitive
• BRN: 3196196
• CAS DataBase Reference: (R)-(+)-2-Phenylglycinol(CAS DataBase Reference)
• NIST Chemistry Reference: (R)-(+)-2-Phenylglycinol(2549-14-6)
• EPA Substance Registry System: (R)-(+)-2-Phenylglycinol(2549-14-6)

Safety Data

• Hazard Codes: C
• Statements: 22-34
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 3259 8/PG 3
• WGK Germany: 3
• F: 3-10-23-34
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 2549-14-6(Hazardous Substances Data)

Usage

Chemical Properties

Light yellow powder

InChI:InChI=1/C8H11NO/c9-6-8(10)7-4-2-1-3-5-7/h1-5,8,10H,6,9H2/t8-/m0/s1

Synthetic route

(R)-2-nitro-1-phenylethanol (145920-96-3) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With hydrogen; palladium on activated charcoal In methanol	100%

<2R-(2α(R*),3aα,4α,7α,7aα)>-β-<(Octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-yl)-oxy>-benzolethanamin → (R)-2-Amino-1-phenylethanol (2549-14-6) + <2S-(2α,3aα,4α,7α,7aα)>-2,3,3a,4,5,6,7,7a-Octahydro-2-methoxy-7,8,8-trimethyl-4,7-methanobenzofuran (81925-10-2)

Conditions	Yield
With hydrogenchloride In methanol	A 97% B 93.5%

(R)-2-azido-1-phenylethanol (134625-72-2) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With hydrogen; palladium on activated charcoal	95%
With lithium aluminium tetrahydride In diethyl ether for 3h; Heating;	90%
With hydrogen; sodium hydroxide In aq. phosphate buffer; water at 30℃; under 7500.75 Torr; for 4h; pH=9; Green chemistry;	87%
With hydrogen; Lindlar's catalyst In ethyl acetate at 25℃; under 2327.2 Torr; for 7h;
With palladium 10% on activated carbon; hydrogen In methanol

2-Aminoacetophenone (613-89-8) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With C30H29N2OP; iron(II) acetate In tetrahydrofuran at 25℃; for 1h; Inert atmosphere;	94%
With Arthrobacter sp. TS-15 recombinant ephedrine dehydrogenase; NADH In aq. phosphate buffer at 25℃; pH=7.5; Kinetics; Green chemistry; Enzymatic reaction; enantioselective reaction;	n/a

(R)-Mandelonitrile (10020-96-9) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With lithium aluminium tetrahydride In diethyl ether for 3h; Ambient temperature;	92%
With lithium aluminium tetrahydride In diethyl ether
Multi-step reaction with 3 steps 1: 65 percent / pyridine / -20 °C 2: I2 / tetrahydrofuran 3: 88 percent / LiAlH4 / tetrahydrofuran / 4 h / 0 °C View Scheme
Multi-step reaction with 2 steps 1: N-methylimidazole / tetrahydrofuran / 3 h / 20 °C 2: 88 percent / LiAlH4 / tetrahydrofuran / 4 h / 0 °C View Scheme

(R)-(-)-2-benzylamino-1-(3-chlorophenyl)ethanol (185035-43-2) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
	92%

(R)-2-(2-hydroxy-2-phenylethyl)isoindoline-1,3-dione → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With hydrazine In water at 60℃;	89%

(R)-2-(diethylphosphoryloxy)-2-phenylacetonitrile (604808-44-8) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran at 20℃;	88%
With lithium aluminium tetrahydride In tetrahydrofuran at 0℃; for 4h;	88%

(2R)-mandelamide (4358-86-5, 4410-31-5, 24008-63-7, 24008-62-6) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran Heating;	84%
With LiAlH In tetrahydrofuran 1.) reflux, 8 h, 2.) r.t., overnight;	78%
With lithium aluminium tetrahydride

(E)-2-oxo-2-phenylacetaldehyde O-methyl oxime (75735-33-0) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With yeast Saccharomyces cerevisiae optical yield given as %ee;	77%

(R)-2-bromo-1-phenylethanol (73908-23-3) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With ammonia In water at 20℃; for 2h;	75%

dl-threo-phenylserine (69-96-5, 1078-17-7, 2584-74-9, 2584-75-0, 6254-48-4, 7352-06-9, 7687-36-7, 7695-56-9, 32946-42-2, 50897-27-3, 68296-26-4, 109120-55-0) + glycine (56-40-6) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
Stage #1: dl-threo-phenylserine; glycine With manganese(ll) chloride In phosphate buffer at 25℃; for 24h; pH=5.5; Stage #2: With Pseudomonas putida L-threonine aldolase In phosphate buffer for 100h; pH=5.5; Further stages.;	57%

(E)-2-oxo-2-phenylacetaldehyde O-methyl oxime (75735-33-0) → (R)-2-hydroxy-2-phenylacetaldehyde O-methyl oxime + C9H13NO2 (1287753-57-4) + (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
Stage #1: (E)-2-oxo-2-phenylacetaldehyde O-methyl oxime With borane-THF; C13H24BNO2 In tetrahydrofuran at 0 - 20℃; for 3.5h; Stage #2: With methanol at 20℃; for 24h;	A 31% B 13% C 3%
With borane-THF; C13H24BNO2 at 20℃; for 18h;

2-Aminoacetophenone (613-89-8) → C16H20N2O2 + (S)-2-Amino-1-phenyl-1-ethanol (56613-81-1) + (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With tetrabutylammonium tetrafluoroborate In N,N-dimethyl-formamide; isopropyl alcohol Electrochemical reaction;	A 9% B n/a C n/a

2-Amino-1-phenylethanol (7568-93-6) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With MANDELIC ACID

hydrogen cyanide (74-90-8) + benzaldehyde (100-52-7) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
(i) (enzymatic transformation), (ii) LiAlH4, Et2O; Multistep reaction;

benzoyl cyanide (613-90-1) → (S)-2-Amino-1-phenyl-1-ethanol (56613-81-1) + (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With sodium tetrahydroborate; B-isopinocampheyl-9-borabicyclo[3.3.1]nonane; cobalt(II) chloride 2.) methanol; Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts;

(2R)-N-ethoxycarbonyl-2-phenyl-2-hydroxyethylamine (144372-49-6) → (S)-2-Amino-1-phenyl-1-ethanol (56613-81-1) + (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With potassium hydroxide In methanol; water for 40h; Heating; Yields of byproduct given. Title compound not separated from byproducts;

(R)-(2-hydroxy-2-phenyl-ethyl)carbamic acid tert-butyl ester (86013-50-5) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With trifluoroacetic acid In water at 25℃; for 0.5h; Yield given;

(R)-benzyl N-(2-hydroxy-2-phenylethyl)carbamate (144372-50-9) → (S)-2-Amino-1-phenyl-1-ethanol (56613-81-1) + (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With potassium hydroxide In methanol; water for 40h; Heating; Yields of byproduct given. Title compound not separated from byproducts;

(R)-(+)-α-<(tert-butyldimethylsilyl)oxy>-benzeneacetonitrile (120390-75-2) → (S)-2-Amino-1-phenyl-1-ethanol (56613-81-1) + (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran for 1h; Heating; Yield given. Yields of byproduct given. Title compound not separated from byproducts;

2-amino-1-phenylethanol hydrochloride (4561-43-7) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Butyric acid (R)-2-butyrylamino-1-phenyl-ethyl ester (144372-51-0) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With potassium hydroxide In methanol; water for 40h; Heating;	260 mg

Butyric acid (S)-2-ethoxycarbonylamino-1-phenyl-ethyl ester (144315-90-2) → (S)-2-Amino-1-phenyl-1-ethanol (56613-81-1) + (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With potassium hydroxide In methanol; water for 40h; Heating; Yields of byproduct given. Title compound not separated from byproducts;

Butyric acid (S)-2-benzyloxycarbonylamino-1-phenyl-ethyl ester (144315-91-3) → (S)-2-Amino-1-phenyl-1-ethanol (56613-81-1) + (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With potassium hydroxide In methanol; water for 40h; Heating; Yields of byproduct given. Title compound not separated from byproducts;

(R)-N-(2-hydroxy-2-phenylethyl)acetamide (149342-37-0) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With hydrogenchloride In methanol
With hydrogenchloride; water at 110℃; for 24h;	0.6 mg

(2S)-N-ethoxycarbonyl-2-phenyl-2-hydroxyethylamine → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With hydrogenchloride In methanol

Thiophene-2-carboxylic acid ((R)-2-hydroxy-2-phenyl-ethyl)-amide (149286-02-2) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With hydrogenchloride In methanol

(-)-N-benzoyl-2-hydroxy-2-phenylethylamine (111059-46-2) → (R)-2-Amino-1-phenylethanol (2549-14-6)

Conditions	Yield
With hydrogenchloride In methanol
With potassium hydroxide In ethanol; water at 80℃; for 8h; Substitution;

di-tert-butyl dicarbonate (24424-99-5) + (R)-2-Amino-1-phenylethanol (2549-14-6) → (R)-(2-hydroxy-2-phenyl-ethyl)carbamic acid tert-butyl ester (86013-50-5)

Conditions	Yield
	100%
In tetrahydrofuran at 20℃;	100%
With triethylamine In dichloromethane at 20℃; for 3h;	99%
In tetrahydrofuran at 20℃; for 3h;	89.1%
In chloroform at 0℃; for 0.5h;

tert-butyl N-{2-[4-(isothiocyanatomethyl)benzamido]phenyl}carbamate (1448350-40-0) + (R)-2-Amino-1-phenylethanol (2549-14-6) → (R)-tert-butyl N-(2-(4-((3-(2-hydroxy-2-phenylethyl)thioureido)methyl)benzamido)phenyl)carbamate (1448350-47-7)

Conditions	Yield
In acetonitrile at 20℃; for 16h;	100%
In tetrahydrofuran at 20℃; for 18h;

(R)-2-Amino-1-phenylethanol (2549-14-6) + acrolein (107-02-8) → C22H26N2O2

Conditions	Yield
In chloroform at 20℃; for 0.166667h; Solvent;	100%

C44H48N4O4(2+)*2Cl(1-) + (R)-2-Amino-1-phenylethanol (2549-14-6) → C60H66N6O4(2+)*2Cl(1-)

Conditions	Yield
In dichloromethane at 20℃; for 20h; Inert atmosphere;	100%

2-(4-aminophenyl)ethyl chloride (81865-10-3) + (R)-2-Amino-1-phenylethanol (2549-14-6) → YM-208876 (391901-45-4)

Conditions	Yield
With triethylamine In methanol at 60 - 65℃; for 8h; Temperature;	97.6%

succinic acid anhydride (108-30-5) + (R)-2-Amino-1-phenylethanol (2549-14-6) → C12H15NO4 (1417721-52-8)

Conditions	Yield
In dichloromethane	97%
In dichloromethane	97%

1,4-dibromo-butane (110-52-1) + (R)-2-Amino-1-phenylethanol (2549-14-6) → (R)-(-)-1-phenyl-2-(pyrrolidin-1-yl)ethanol (87069-57-6)

Conditions	Yield
With sodium hydrogencarbonate In toluene at 105 - 118℃; Dean-Stark; Inert atmosphere;	97%

1-(ethoxycarbonylmethyl)benzimidazole (55175-50-3) + (R)-2-Amino-1-phenylethanol (2549-14-6) → (R)-N-(2-hydroxy-1-phenylethyl)-2-(1H-benzo[d]-imidazol-1-yl) acetamide

Conditions	Yield
In toluene at 180℃; for 0.166667h; Microwave irradiation;	96%

(R)-2-Amino-1-phenylethanol (2549-14-6) + 2-(2-aminothiazol-5-yl)-N-[4-(2-chloroethyl)phenyl]acetamide → mirabegron

Conditions	Yield
With triethylamine In methanol at 60 - 65℃; for 8h; Solvent;	96%

piperonal (120-57-0) + (R)-2-Amino-1-phenylethanol (2549-14-6) → (R)-E-β-((1, 3-benzodioxol-5-ylmethylene)amino)benzene-ethanol (179930-11-1)

Conditions	Yield
With toluene-4-sulfonic acid In toluene Reflux; Dean-Stark; Large scale;	95.4%

2-formylbenzene boronic acid (40138-16-7) + (R)-2-Amino-1-phenylethanol (2549-14-6) → (C6H4CHNCH2CH(C6H5)O)2B2O

Conditions	Yield
In chloroform byproducts: H2O; B compd. stirred with aminoalcohol in CHCl3 at room temp. for 10 min; solvent removed under reduced pressure;	95%
In chloroform for 0.166667h;	95%

(R)-2-Amino-1-phenylethanol (2549-14-6) + malonic acid dimethyl ester (108-59-8) → N,N'-bis[(R)-1-phenyl-2-hydroxyethyl]propane-1,3-diamide

Conditions	Yield
With lithium methanolate In n-heptane at 100℃; for 3h;	94%

(R)-2-Amino-1-phenylethanol (2549-14-6) + N-(4-fluoro-3-nitro-phenyl)-N-methyl-benzamide (658700-09-5) → N-[4-((R)-2-hydroxy-2-phenyl-ethylamino)-3-nitro-phenyl]-N-methyl-benzamide (863409-16-9)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In DMF (N,N-dimethyl-formamide) at 20 - 85℃; for 24h;	93.4%

(R)-2-Amino-1-phenylethanol (2549-14-6) + 1,1'-carbonyldiimidazole (530-62-1) → (5R)-5-phenyl-1,3-oxazolidin-2-one (54705-41-8)

Conditions	Yield
With 1H-imidazole In dichloromethane at 20℃; for 16h;	92%

3-formyl-furan-2-ylboronic acid (27339-38-4) + (R)-2-Amino-1-phenylethanol (2549-14-6) → (OC4H2CHNCH2CH(C6H5)O)2B2O

Conditions	Yield
In chloroform byproducts: H2O; B compd. stirred with aminoalcohol in CHCl3 at room temp. for 10 min; solvent removed under reduced pressure;	92%
In chloroform for 0.166667h;	92%

N-(quinolin-8-yl)but‐3‐enamide + (R)-2-Amino-1-phenylethanol (2549-14-6) → 3-(((R)-2-hydroxy-2-phenylethyl)amino)-N-(quinolin-8-yl)butanamide

Conditions	Yield
With cesium acetate at 100℃; for 24h; Schlenk technique; chemoselective reaction;	92%

(R)-2-(2-(4-chlorobenzylamino)-2-oxoethyl)pent-4-enoic acid (1201482-21-4) + (R)-2-Amino-1-phenylethanol (2549-14-6) → C22H25ClN2O3 (1201482-32-7)

Conditions	Yield
Stage #1: (R)-2-(2-(4-chlorobenzylamino)-2-oxoethyl)pent-4-enoic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 0℃; for 0.5h; Stage #2: (R)-2-Amino-1-phenylethanol With dmap In N,N-dimethyl-formamide at 0 - 20℃;	91%

2,2'-bis-(bromomethyl)-1,1'-biphenyl (38274-14-5) + (R)-2-Amino-1-phenylethanol (2549-14-6) → (R)-2-(5H-dibenzo[c,e]azepin-6(7H)-yl)-1-phenylethanol

Conditions	Yield
With triethylamine In acetonitrile for 24h; Reflux;	91%

Burgess Reagent (29684-56-8) + (R)-2-Amino-1-phenylethanol (2549-14-6) → (S)-1,1-Dioxo-3-phenyl-1λ6-[1,2,5]thiadiazolidine-2-carboxylic acid methyl ester

Conditions	Yield
In tetrahydrofuran at 0 - 25℃; for 6h;	90%
at 0 - 25℃; for 6h;	90%

1,3-propanesultone (1120-71-4) + (R)-2-Amino-1-phenylethanol (2549-14-6) → 3-{[(2R)-2-hydroxy-2-phenylethyl]amino}-2-propanesulfonic acid

Conditions	Yield
In toluene; acetonitrile for 4h; Heating / reflux;	90%

3-(3,5-ditrifluoromethylphenylamino)-4-methoxybutane-3-en-1,2-dione (1223105-85-8) + (R)-2-Amino-1-phenylethanol (2549-14-6) → C20H14F6N2O3

Conditions	Yield
In methanol at 20℃; for 24h; Inert atmosphere;	90%

di-tert-butyl dicarbonate (24424-99-5) + (R)-2-Amino-1-phenylethanol (2549-14-6) → [(R)-2-phenyl-propyl]-carbamic acid tert-butyl ester

Conditions	Yield
In tetrahydrofuran at 20℃; for 3h;	89.1%

1-isoquinolinecarboxylic acid (486-73-7) + (R)-2-Amino-1-phenylethanol (2549-14-6) → (R)-(-)-N-(2-hydroxy-2-phenylethyl)isoquinoline-1-carboxamide

Conditions	Yield
Stage #1: 1-isoquinolinecarboxylic acid With triethylamine; methyl chloroformate In tetrahydrofuran at 20 - 22℃; for 2h; Stage #2: (R)-2-Amino-1-phenylethanol With triethylamine In tetrahydrofuran at 0 - 22℃;	89%
Stage #1: 1-isoquinolinecarboxylic acid With triethylamine; methyl chloroformate In tetrahydrofuran at 0℃; Inert atmosphere; Stage #2: (R)-2-Amino-1-phenylethanol With triethylamine In tetrahydrofuran at 0 - 20℃; Inert atmosphere;	89%

Upstream product

• 4358-86-5 (2R)-mandelamide 
• 7568-93-6 2-Amino-1-phenylethanol 
• 74-90-8 hydrogen cyanide 
• 100-52-7 benzaldehyde 
• 144372-50-9 (R)-benzyl N-(2-hydroxy-2-phenylethyl)carbamate 
• 120390-75-2 (R)-(+)-α-<(tert-butyldimethylsilyl)oxy>-benzeneacetonitrile 
• 124718-87-2 2-azido-1-phenylethan-1-ol 
• 20780-53-4 (R)-Styrene oxide 
• 69-96-5 dl-threo-phenylserine 
• 56-40-6 glycine 
• 5468-37-1 2-aminoacetophenone hydrochloride 
• 613-89-8 2-Aminoacetophenone 
• 86087-13-0 4,6-dimethyl-2-phenyl-(2α,4α,6β)-1,3-dioxane 
• 107171-75-5 (R)-2-(benzylamino)-1-phenylethan-1-ol 

Downstream Products

• 130406-45-0 -carbamic acid <2-<(2-hydroxy-2-phenylethyl)amino>-1-(1H-indol-3-ylmethyl)-1-methyl-2-oxoethyl>-tricyclo<3.3.1.1^3,7>dec-2-yl ester 
• 84619-59-0 (-)-2-cyclohexyl-2-hydroxyethylamine 
• 1236005-70-1 2-{[(Z)-(R)-2-Hydroxy-2-phenyl-ethylimino]-methyl}-phenol 
• 191043-23-9 (5R)-5-phenyl-1,3-oxazolidine-2-thione 
• 156317-12-3 (+)-(2R,2'R,2''R)-triphenylethan-2-olamine 
• 14467-49-3 (R)-(-)-α-<<(1-methylethyl)amino>methyl>benzenemethanol 
• 848410-00-4 4-(2-hydroxy-2-phenyl-ethylamino)-piperidine-1-carboxylic acid tert-butyl ester 
• 54705-41-8 (5R)-5-phenyl-1,3-oxazolidin-2-one 
• 144372-50-9 (R)-benzyl N-(2-hydroxy-2-phenylethyl)carbamate 

Relevant articles and documents

Method for synthesizing chiral alpha-amino alcohol compound

The invention discloses a method for synthesizing a chiral alpha-amino alcohol compound. The method comprises the following steps: sequentially adding an iron catalyst, a ligand, ketone, an organic solvent and silane into a reaction system at 20-30 DEG C in a nitrogen atmosphere, then stirring the obtained mixture, and carrying out column chromatography separation on the obtained product to obtain a product, namely chiral alpha-amino alcohol. According to the invention, the most high-yield iron catalyst in earth crust is used, and cheap silane (PMHS, 500 g/298 yuan) is adopted as a reducing agent, so the asymmetric reduction reaction of alpha-amino ketone can be efficiently achieved under mild conditions so as to obtain the high-yield optically-active chiral alpha-amino alcohol compound; and moreover, through the creative labor of the inventor, reaction yield can reach 99%, and meanwhile, the content of the target product in the generated reaction product is 99%.

Two enantiocomplementary ephedrine dehydrogenases from arthrobacter sp. TS-15 with broad substrate specificity

The recently identified pseudoephedrine and ephedrine dehydrogenases (PseDH and EDH, respectively) from Arthrobacter sp. TS-15 are NADH-dependent members of the oxidoreductase superfamily of short-chain dehydrogenases/reductases (SDRs). They are specific for the enantioselective oxidation of (+)-(S) N-(pseudo)ephedrine and (-)-(R) N-(pseudo)ephedrine, respectively. Anti-Prelog stereospecific PseDH and Prelog-specific EDH catalyze the regio- A nd enantiospecific reduction of 1-phenyl-1,2-propanedione to (S)-phenylacetylcarbinol and (R)-phenylacetylcarbinol with full conversion and enantiomeric excess of >99%. Moreover, they perform the reduction of a wide range of aryl-aliphatic carbonyl compounds, including ketoamines, ketoesters, and haloketones, to the corresponding enantiopure alcohols. The highest stability of PseDH and EDH was determined to be at a pH range of 6.0-8.0 and 7.5-8.5, respectively. PseDH was more stable than EDH at 25 °C with half-lives of 279 and 38 h, respectively. However, EDH is more stable at 40 °C with a 2-fold greater half-life than at 25 °C. The crystal structure of the PseDH-NAD+ complex, refined to a resolution of 1.83 ?, revealed a tetrameric structure, which was confirmed by solution studies. A model of the active site in complex with NAD+ and 1-phenyl-1,2-propanedione suggested key roles for S143 and W152 in recognition of the substrate and positioning for the reduction reaction. The wide substrate spectrum of these dehydrogenases, combined with their regio- A nd enantioselectivity, suggests a high potential for the industrial production of valuable chiral compounds.

Highly efficient enantioselective liquid-liquid extraction of 1,2-amino-alcohols using SPINOL based phosphoric acid hosts

Access to enantiopure compounds on large scale in an environmentally friendly and cost-efficient manner remains one of the greatest challenges in chemistry. Resolution of racemates using enantioselective liquid-liquid extraction has great potential to meet that challenge. However, a relatively feeble understanding of the chemical principles and physical properties behind this technique has hampered the development of hosts possessing sufficient resolving power for their application to large scale processes. Herein we present, employing the previously untested SPINOL based phosphoric acids host family, an in depths study of the parameters affecting the efficiency of the resolution of amino-alcohols in the optic of further understanding the core principles behind ELLE. We have systematically investigated the dependencies of the enantioselection by parameters such as the choice of solvent, the temperature, as well as the pH and bring to light many previously unsuspected and highly intriguing interactions. Furthermore, utilizing these new insights to our advantage, we developed novel, highly efficient, extraction and resolving protocols which provide remarkable levels of enantioselectivity. It was shown that the extraction is catalytic in host by demonstrating transport in a U-tube and finally it was demonstrated how the solvent dependency could be exploited in an unprecedented triphasic resolution system.