The optically active benzylamine derivatives of the present invention are very useful for use as the asymmetric ligand of an asymmetric reducing agent. By using the optically active amine-boron complex prepared from the compound of the present invention, optically active products can be obtained in a specifically high optical yield. Moreover, the separation and recovery of the reaction products and asymmetric ligand can be easily achieved.

The present invention relates to a novel optically active 
hydroxybenzylamine derivative represented by the formula (I) 
##STR1## 
wherein R.sup.1 denotes a hydrogen atom, lower alkyl group or lower alkoxy 
group; R.sup.2 denotes a lower alkyl group; * signifies an asymmetric 
carbon atom; and the hydroxyl group is located on the phenyl at the ortho- 
or metaposition relative to the substituent having the asymmetric carbon, 
an optically active amine-boron compound having said derivative as a 
ligand, and 
a process for producing an optically active compound by using said 
compound. 
Optically active benzylamine derivatives so far known include 
.alpha.-phenethylamine, and .alpha.-p-hydroxyphenylethylamine wherein the 
hydroxyl group is located at the para-position on the phenyl. It is also 
known that the former can be used as an asymmetric ligand for asymmetric 
reduction and the latter can be used as a resolving agent (see, for 
example, J. Chem. Soc., Perkin Trans., I, 371 (1978); J. Chem. Soc., 99, 
416 (1911)). 
However, nothing has yet been known about an optically active 
hydroxybenzylamine derivative represented by the formula (I) shown above 
wherein the hydroxyl group is located at the ortho- or meta-position on 
the phenyl group. 
Further, the use of the above-mentioned optically active 
.alpha.-phenethylamine as the asymmetric ligand of asymmetric reducing 
agent accompanies such disadvantages that the optical yield of optically 
active compounds obtained by reduction is low, or the reduction products 
cannot be easily separated from the ligand. 
The present inventors have synthesized various optically active benzylamine 
derivatives and, after extensive studies thereon, found that an optically 
active benzylamine derivative wherein the hydroxyl group is located at a 
specific position, namely orthoor meta-position, on the phenyl group, when 
used as an asymmetric ligand of asymmetric reducing agent, gives a 
reduction product in a very high optical yield and yet can be separated 
from the reaction product very easily. The present invention has been 
accomplished on the basis of the above finding and additional extensive 
studies. 
Thus, according to the present invention, there are provided a novel 
optically active hydroxybenzylamine derivative represented by the formula 
(I) 
##STR2## 
wherein R.sup.1 denotes a hydrogen atom, lower alkyl group or lower alkoxy 
group; R.sup.2 denotes a lower alkyl group; * signifies an asymmetric 
carbon atom; and the hydroxyl group is located on the phenyl at the ortho- 
or metaposition relative to the substituent having the asymmetric carbon 
atom, 
an optically active amine-boron compound having said derivative as a 
ligand, and 
a process for producing an optically active compound by using said 
compound. 
The optically active hydroxybenzylamine derivative of the present invention 
is represented by the above formula (I). Preferably, the hydroxyl group is 
located at the ortho-position relative to the substituent having the 
asymmetric carbon atom. 
Specific examples of the groups denoted by R.sup.1 include hydrogen; lower 
alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 
isobutyl, sec-butyl, t-butyl, pentyl and hexyl; and lower alkoxy groups 
such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, 
sec-butoxy, n-pentyloxy and n-hexyloxy. 
Specific examples of the groups denoted by R.sup.2 include the same lower 
alkyl groups as those mentioned for R.sup.1. 
Specific examples of the compounds of the present invention, there may be 
mentioned optically active 1-(2-hydroxy-3-ethylphenyl)ethylamine, 
1-(2-hydroxy-3-methylphenyl)ethylamine, 
1-(2-hydroxy-3-methoxyphenyl)ethylamine, 
1-(2-hydroxy-3-ethoxyphenyl)ethylamine, 
1-(2-hydroxy-5-methoxyphenyl)ethylamine, 1-(2-hydroxyphenyl)ethylamine, 
1-(2-hydroxy-5-ethoxyphenyl)ethylamine, 1-(2-hydroxyphenyl)propylamine, 
1-(3-hydroxyphenyl)ethylamine, 1-(2-hydroxy-3-ethylphenyl)propylamine, 
1-(2-hydroxy-3-methylphenyl)propylamine, 
1-(2-hydroxy-3-methylphenyl)propylamine 
1-(2-hydroxy-3ethylphenyl)propylamine, 
1-(2-hydroxy-3-methoxyphenyl)propylamine, 
1-(2-hydroxy-3-ethoxyphenyl)propylamine, 
1-(2-hydroxy-5-methylphenyl)ethylamine, 
1-(2-hydroxy5-ethylphenyl)ethylamine, 
1-(2-hydroxy-5-methoxyphenyl)propylamine, 
1-(2-hydroxy-5-ethoxyphenyl)propylamine, 
1-(2-hydroxy-4-methylphenyl)ethylamine, 
1-(2-hydroxy-4-methoxyphenyl)ethylamine, 
1-(2-hydroxy-4-methylphenyl)propylamine, 
1-(2-hydroxy4-methoxyphenyl)propylamine, 1-(3-hydroxyphenpropylamine, 
1-(2-hydroxy-6-methylphenyl)ethylamine, 
1-(2-hydroxy-6-methoxyphenyl)ethylamine, 
1-(2-hydroxy-6-methylphenyl)propylamine, and 
1-(2-hydroxy-6-methoxyphenyl)propylamine. 
Such optically active benzylamine derivatives (I) may be prepared, for 
example, through the following route. 
##STR3## 
In a more specific example, a ketone compound of the formula (VI) and a 
benzyl halide are converted into a benzyl compound of the formula (VII) by 
Williamson synthesis, which is then allowed to react with hydroxylamine or 
alkoxylamines in such a solvent as pyridine to form an oxime compound of 
the formula (VIII), and then subjected to asymmetric reduction to prepare 
an optically active amine of the formula (IX). The above asymmetric 
reduction may be conducted, for example, with reference to the method 
described in J. Chem. Soc., Perkin Trans., I, 2039 (1985). For example, 
the compounds of the formula (I) can also be used as an asymmetric ligand. 
The optically active amines of the formula (IX) may also be obtained by 
catalytically hydrogenating the oxime compound of the formula (VIII) with 
the aid of a hydrogenation catalyst such as palladium, platinum or Raney 
nickel, or by reducing said oxime compound with a metal hydride such as 
lithium aluminum hydride, sodium borohydride, borane.tetrahydrofuran 
complex and borane. dimethyl sulfide complex, to obtain a racemic amine of 
the formula (IX), followed by subjecting the amine to optical resolution. 
The optically active benzylamine derivative of the formula (I) may then be 
obtained by subjecting the optically active amine of the formula (IX) to 
hydrogenolysis. 
The hydrogenolysis can be accomplished by using conventional methods. For 
example, it is conducted in the presence of a catalyst such as palladium, 
platinum or Raney nickel. 
The optically active amines (IX) may be used also in the form of their 
acids with mineral acids such as hydrochloric acid and sulfuric acid or 
organic acids such as acetic acid and propionic acid. 
Though the solvent to be used is not particularly restricted so long as it 
does not poison the catalyst, usually alcohols such as methanol, ethanol 
and isopropanol or solvent mixtures thereof with water are used. When 
catalysts other than Raney nickel are used, the reaction may also be 
conducted in the presence of mineral acids such as hydrochloric acid and 
sulfuric acid or organic acids such as acetic acid and propionic acid. 
Although the reaction is usually carried out at -50.degree. to +60.degree. 
C. and at 0 to 150 kg/cm.sup.2, it may be satisfactorily conducted at room 
temperature and at normal pressure. 
Hereunder, the process for producing the amine-boron compound of the 
present invention having the optically active benzylamine derivative (I) 
as a ligand, and the process for producing optically active compounds by 
using the compound will be described. 
The amine-boron compound of the present invention may be prepared, for 
example, from the derivative (I) and a boron hydride compound such as 
diborane, borane.tetrahydrofuran complex and borane.dimethyl sulfide 
complex. The molar ratio of the boron hydride compound to the number of 
moles of boron contained in the derivative (I) is normally 1 to 5, 
preferably 2 to 3. 
There is no particular restriction as to the solvent so long as the solvent 
does not participate in the reaction. Specific examples of the solvents 
include ethers or thioethers such as diethyl ether, tetrahydrofuran, 
diglyme, and dimethyl sulfide; aromatic hydrocarbons such as benzene, 
toluene, xylene and chlorobenzene; halogenated hydrocarbons such as 
methylene chloride, 1,2-dichloroethane, chloroform, and carbon 
tetrachloride; and the solvent mixtures thereof. 
The preparation is usually carried out at a temperature of -78.degree. to 
+100.degree. C., preferably -40.degree. to +50.degree. C. and normally in 
an atmosphere of inert gas such as nitrogen and argon. 
Thus, the amine-boron compound of the present invention which has the 
derivative (I) as a ligand is prepared. The compound is highly fitted for 
use as an asymmetric reducing agent. For example, when asymmetric 
ketoximes or asymmetric ketones are reacted therewith, optically active 
amines are obtained from the former and optically active alcohols are 
obtained from the latter, respectively, in a high optical yield. Moreover, 
the separation of the reduction product from the ligand can be 
accomplished in simple operations of pH adjustment and liquid layer 
separation. 
Firstly, the asymmetric reduction of prochiral ketoximes will be described. 
As an example, optically active amines represented by the formula (IV) can 
be prepared from the anti-form or syn-form isomer of oximes represented by 
the formula (II) or mixtures rich in either one of the isomers. 
##STR4## 
wherein R.sup.3 denotes a hydrogen atom, alkyl group, aralkyl group or 
alkyl-substituted silyl group; R.sup.4 and R.sup.5 are different from each 
other and each denotes a lower alkyl group, aryl group or aralkyl group; 
and * signifies an asymmetric carbon atom. 
As examples of the substituent R.sup.3 in oximes (II), there may be 
mentioned alkyl groups of 1 to 10 carbon atoms such as methyl, ethyl, 
propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, 
cycloheptyl, octyl, cyclooctyl, nonyl, and decyl; aralkyl groups of 7 to 
11 carbon atoms such as benzyl, .beta.-phenethyl and naphthylmethyl; and 
alkylsilyl groups of 3 to 12 carbon atoms such as trimethylsilyl, 
dimethyl-t-butylsilyl, tri-n-propylsilyl and tri-n-butylsilyl. 
As examples of the substituents R.sup.4 and R.sup.5, there may be mentioned 
aryl groups of 5 to 17 total carbon atoms including phenyl, 2-, 3- and 
4-pyridyl; halogen-substituted phenyls such as o-, m- and p-chlorophenyl, 
o-, m- and p-bromophenyl and 2,3-, 2,4-, 2,5-, and 2,6-dichlorophenyl; 
phenyls substituted with C.sub.1 -C.sub.6 alkyls such as o-, m- and 
p-methylphenyl, o-, m-and p-ethylphenyl, o-, m- and p-butylphenyl and 
2,3-, 2,4-, 2,5- and 2,6-dimethylphenyl; phenyls substituted with C.sub.1 
-C.sub.6 alkoxyls such as o-, m- and p-methoxyphenyl, o-, m- and 
p-ethoxyphenyl, and o-, m- and p-propoxyphenyl; benzyloxy-substituted 
phenyls such as o-, m- and p-benzyloxyphenyl, 2-benzyloxy-3-methylphenyl, 
2-benzyloxy-4-methylphenyl, 2-benzyloxy-5-methylphenyl, 
2-benzyloxy5-t-butylphenyl, 2-benzyloxy-3-methoxyphenyl, 
2-benzyloxy-4-methoxyphenyl, 2-benzyloxy-5-methoxyphenyl, and 
2-benzyloxy-3,5-dichlorophenyl; and .alpha.- and .beta.- naphthyl; lower 
alkyl groups of 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, 
pentyl, cyclopentyl, hexyl and cyclohexyl; and aralkyl groups of 7 to 11 
carbon atoms such as benzyl, o-, m- and p-tolylmethyl, (o-, m- and 
p-ethylphenyl)methyl, (2,3-, 2,4-, 2,5- and 2,6-dimethylphenyl)methyl, 
2-phenylethyl, 2-(o-, m- and p-tolyl)ethyl, (2,3-, 2,4-, 2,5- and 
2,6-dimethylphenyl)ethyl, 3-phenylpropyl and naphthylmethyl. 
Typical examples of ketoximes include O-methyl-, O-octyl-, O-cyclohexyl-, 
O-benzyl-, and O-trimethylsilyl-oximes or like oximes of acetophenone, 
propiophenone, butyrophenone, isobutyrophenone, 2-acetylpyridine, 
o-methoxyacetophenone, o-ethoxyacetophenone, o-propoxyacetophenone, 
o-benzyloxyacetophenone, .alpha.-acetonaphthone, .beta.-acetonaphthone, 
phenyl benzyl ketone, phenyl p-tolylmethyl ketone, phenyl m-tolylmethyl 
ketone, phenyl o-tolylmethyl ketone, phenyl 2-phenylethyl ketone, 
2-butanone, 2-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 2-octanone, 
3-heptanone, 3-octanone, cyclohexyl methyl ketone, cyclohexyl ethyl 
ketone, cyclohexyl benzyl ketone, .alpha.-phenylacetone, 2-phenylethyl 
methyl ketone, 2-phenylethyl ethyl ketone, 3-phenylpropyl methyl ketone 
and the like. The syn-form or anti-form isomer of these oximes or mixtures 
thereof rich in either one of the isomers are used. 
These ketoximes may be easily prepared from the corresponding ketones by 
well-known methods. When only one of the syn-form and anti-form isomers is 
used, the other isomer remaining after separation can be converted to the 
required isomer by syn/anti isomerization in a conventional manner, 
whereby effective utilization of the raw material can be achieved. 
In the asymmetric reduction of prochiral ketoximes, the reducing agent is 
applied to the ketoximes in an amount of at least equivalent moles, 
usually 1 to 6 times by mole, as calculated in terms of the derivative 
(I). One to three times by mole is usually satisfactory for the purpose. 
Solvents used in the reduction is not specifically restricted so long as 
they are inert ones which do not participate in the reduction. Examples of 
such solvents include aromatic hydrocarbons such as benzene, toluene, 
xylene and chlorobenzene; halogenated hydrocarbons such as methylene 
chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride; ether 
such as diethyl ether, tetrahydrofuran, dioxane, and diglyme; and solvent 
mixtures thereof. The amount of the solvent used is generally 2 to 50 
times by weight based on the ketoximes. 
The solvent which has been used in the step of preparing the reducing agent 
may be used as such, or after replenished with above-stated solvent, as 
the solvent for the reduction step. 
The reduction in normally carried out in an inert gas atmosphere similar to 
that stated before. The reaction temperature is usually -30.degree. to 
+100.degree. C. and, in commercial production, generally -10.degree. to 
+50.degree. C. 
After completion of the reduction, in general, an aqueous solution of a 
mineral acid such as hydrochloric acid is added to the reaction liquid to 
decompose the reducing agent. The resulting liquid is then made alkaline 
with an aqueous alkali solution such as aqueous caustic soda solution and 
separated into layers. The optically active amines, the intended reduction 
products, are recovered from the organic layer. On the other hand, the 
aqueous layer is neutralized with a mineral acid such as hydrochloric 
acid, or once acidified and then neutralized with an aqueous solution of 
an alkali such as ammonia, sodium hydrogen carbonate or sodium carbonate, 
and thereafter extracted with an organic solvent, whereby the optically 
active benzylamine derivative (I), the ligand, can be recovered in good 
yield without undergoing racemization, which may be reused as desired. 
Then, the asymmetric reduction of prochiral ketones will be described 
below. As an example, optically active alcohols represented by the formula 
(V) can be prepared from ketones represented by the formula (III). 
##STR5## 
wherein R.sup.6 and R.sup.7 are different from each other and each denotes 
a lower alkyl group, aryl group, aralkyl group, or 2-substituted 
1-triazolylethylene group represented by the formula (VI) 
##STR6## 
wherein R.sup.8 denotes a cyclohexyl group, or a phenyl group which may be 
substituted with a halogen or haloalkyl group; and * signifies an 
asymmetric carbon atom. 
Examples of the substituents R.sup.6 and R.sup.7 include the same lower 
alkyl groups, aryl groups and aralkyl groups as mentioned for R.sup.4 and 
R.sup.5 in the formulas (II) and (III), and 2-substituted 
1-triazolylethylene group having, as the substituent R.sup.8, phenyl, 
chlorophenyl, bromophenyl, dichlorophenyl, dibromophenyl, 
trifluoromethylphenyl, trichloromethylphenyl, tribromomethylphenyl, 
cyclohexyl, and the like. 
As examples of typical ketones, there may be mentioned acetophenone, 
propiophenone, butyrophenone, isobutyrophenone, .alpha.-acetonaphthone, 
.beta.-acetonaphthone, phenyl benzyl ketone, phenyl p-tolylmethyl ketone, 
phenyl m-tolylmethyl ketone, phenyl o-tolylmethyl ketone, 2-butanone, 
2-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 2-octanone, 
1-phenyl-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one, 
1-(4-chlorophenyl)-2-1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one, 
1-(2,4-dichlorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one, 
1-cyclohexyl-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one, 
1-(4-trifluoromethylphenyl)-2-(1,2,4-triazol-1-yl)-4,4-demethyl-1-penten-3 
one, 1-(3-bromophenyl)-2-(1,2,4-triazol-1yl)-4,4-dimethyl-1-penten-3one and 
1-(4-fluorophenyl)-2-(1,2,4-triazol-1-yl)-4,4-dimethyl-1-penten-3-one. 
In the asymmetric reduction of ketones, the reducing agent is applied to 
the ketones in an amount of at least 0.5 time by mole, usually 0.5 to 6 
times by mole, as calculated in terms of the derivative (I). Usually 1 to 
3 times by mole is satisfactory for the purpose. 
Solvents used in the reduction are not specifically restricted so long as 
they are inert ones which do not participate in the reduction. Examples 
thereof include aromatic hydrocarbons such as benzene, toluene, xylene and 
chlorobenzene; halogenated hydrocarbons such as methylene chloride, 
1,2-dichloroethane, chloroform and carbon tetrachloride; esters such as 
diethyl ether, tetrahydrofuran, dioxane and diglyme; and the solvent 
mixtures thereof. The solvent which has been used in the step of preparing 
the reducing agent may be used as such, or after replenished with the 
above-stated solvent, as the solvent for the reduction step. The amount of 
the solvent used is in general 2 to 50 times by weight based on the 
ketones. 
The reduction is normally carried out in an inert gas atmosphere similar to 
that stated before. The reaction temperature is usually -30.degree. to 
+100.degree. C. and, in commercial production, generally -10.degree. to 
+50.degree. C. 
After completion of the reduction, in general, an aqueous solution of a 
mineral acid such as hydrochloric acid is added to the reaction liquid to 
decompose the reducing agent. The resulting liquid is then separated into 
layers under acid conditions. The optically active alcohols, the intended 
reduction products, are recovered from the organic layer. On the other 
hand, the aqueous layer is neutralized with an aqueous solution of alkali 
such as ammonia, sodium hydrogen carbonate or sodium carbonate and then 
extracted with an organic solvent, whereby the optically active 
benzylamine derivative (I) of the ligand can be recovered in good yield 
without undergoing racemization, which may be reused as desired. 
The optically active benzylamine derivatives of the present invention are 
very useful for use as the asymmetric ligand of an asymmetric reducing 
agent. By using the optically active amine-boron complex prepared from the 
compound of the present invention, optically active reduction products can 
be obtained in a specifically high optical yield and moreover the 
separation and recovery of the reaction products and asymmetric ligand can 
be accomplished very easily.

The present invention will be described in detail below with reference to 
the following examples, but it is not limited to these examples. 
REFERENTIAL EXAMPLE 1 
Preparation of Benzyl Compound 
A sodium ethylate solution was prepared from 200 ml of ethanol and 7.9 g 
(0.3435 g-atom) of metallic sodium. Then 0.312 mole (42.52 g) of 
2-hydroxyacetophenone and 47.47 g (0.375 mole) of benzyl chloride were 
added thereto, and the resulting mixture was stirred under reflux for 4 
hours. 
The reaction mixture was then cooled down to room temperature and the 
sodium chloride formed was filtered off. The filtrate was concentrated 
under reduced pressure and extracted with toluene. The toluene extract was 
washed with water, dried and then distilled under reduced pressure to 
obtain 66.06 g of 2-benzyloxyacetophenone. 
In place of 2-hydroxyacetophenone, there were used 2-hydroxypropiophenone, 
2-hydroxy-3-methylacetophenone, 2-hydroxy-3-methoxyacetophenone, 
2-hydroxy5-methoxyacetophenone and 3-hydroxyacetophenone to obtain the 
corresponding benzyl compounds. 
TABLE 1 
______________________________________ 
##STR7## 
Benzyl compound 
Yield 
No. R.sup.1 R.sup.2 (%) B.p. (.degree.C./mmHg) 
______________________________________ 
1 H CH.sub.3 94 140-142/0.3 
2 H C.sub.2 H.sub.5 
90 140-144/0.2 
3 3-CH.sub.3 CH.sub.3 80 127-132/0.3 
4 3-OCH.sub.3 
CH.sub.3 56 160-161/0.6 
5 5-OCH.sub.3 
CH.sub.3 75 162-163/0.3 
6 3-Benzyloxyacetophenone 
91 155/0.3 
______________________________________ 
REFERENTIAL EXAMPLE 2 
Preparation of Oxime Compound 
To 50 ml of pyridine were added 0.0434 mole (9.77 g) of 
2-benzyloxyacetophenone prepared in the first and second paragraphs in 
Referential Example 1 (Table 1, No. 1) and 4.35 g (0.0521 mole) of 
O-methylhydroxylamine hydrochloride. The mixture was stirred at room 
temperature for 2 hours and then at 100.degree. C. for 1 hour. The 
reaction liquid was cooled down to room temperature, 300 ml of water was 
added thereto, and the oil layer was separated off. The aqueous layer was 
extracted with chloroform and the extract was combined with said oil 
layer, washed with water, dried and distilled under reduced pressure to 
obtain 10.77 g of 2-benzyloxyacetophenone O-methyloxime. 
In the same manner but by using the benzyl compounds shown in the third 
paragraph in Referential Example 1 (Table 1, Nos. 2-6), the corresponding 
oxime compounds were obtained. 
TABLE 2 
______________________________________ 
##STR8## 
Oxime 
No. R.sup.1 R.sup.2 
Anti/Syn 
B.p. (.degree.C./mmHg) 
Yield (%) 
______________________________________ 
1 H CH.sub.3 
88/12 135-141/0.2 
97 
2 H C.sub.2 H.sub.5 
80/20 133-140/0.2 
94 
3 3-CH.sub.3 
CH.sub.3 
87/13 127-132/0.3 
97 
4 3-OCH.sub.3 
CH.sub.3 
88/12 150-154/0.4 
97 
5 5-OCH.sub.3 
CH.sub.3 
86/14 155-158/0.3 
97 
6 3-Benzyloxy- 
96/4 147/0.2 95 
acetophenone 
O-methyloxime 
______________________________________ 
REFERENTIAL EXAMPLE 3 
Preparation of Optically Active .alpha.-(Benzyloxyphenyl)-alkylamine 
(3-1) (+)-2-(2-Benzyloxyphenyl)ethylamine 
A mixture of 200 ml of tetrahydrofuran (THF) and 13.79 g (0.054 mole) of 
(S)(-)-2-amino-3-methyl-1,1-diphenylbutanol was cooled to -78.degree. C. 
Then 4.31 g of borane dimethyl sulfide complex was added thereto with 
stirring, and the temperature of the mixture was raised to room 
temperature over a period of about 2 hours. Then, 4.31 g of borane 
dimethyl sulfide complex was further added to the mixture, which was then 
stirred for 15 minutes. 
Then, a mixture of 9.19 g (0.036 mole) of 2-benzyloxyacetophenone 
O-methyloxime obtained in the first paragraph in Referential Example 2 
(Table 2, No. 1) and 10 ml of THF was added thereto and the resulting 
mixture was stirred at room temperature for 20 hours and then at 
60.degree. C. for 1 hour. 
Then, 70 ml of 10% hydrochloric acid was added to the mixture and stirred 
at 50.degree. C. for 1.5 hours. The reaction liquid was concentrated under 
reduced pressure, made alkaline by addition of 10% aqueous sodium 
hydroxide solution, and extracted twice with chloroform. The organic layer 
was washed with water, dried, concentrated, and subjected to silica gel 
column chromatography with ethyl acetate as the eluting solvent, to 
separate and remove the ligand. Thus, 6.08 g of 
(+)-1-(2-benzyloxyphenyl)ethylamine was obtained. 
.sup.1 H-NMR spectrum [.delta.ppm, CDCl.sub.3 ]; 
1.41 (3H, d), 2.16 (2H, s), 4.43 (1H, q), 
5.08 (2H, s), 6.89-7.00 (2H, m), 7.12-7.23 (1H, m), 
7.28-7.44 (7H, m) 
The hydrochloride of the above amine showed an optical rotation 
[.alpha..pi..sub.D .sup.20 of +13.45.degree. (C. 1.05, water). 
The hydrochloride was recrystallized from isopropanol to obtain 4.64 g of 
crystals having an [.alpha.].sub.D.sup.20 of +16.44.degree. (C. 1.09, 
water). A part thereof was reacted with 3,5-dinitrophenyl isocyanate to be 
converted into its urea derivative, which was then analyzed by high 
performance liquid chromatography with an optically active column. It was 
found that the optical purity was 87.2%. 
(3-2) (+)-1-(2-Benzyloxyphenyl)propylamine 
A mixture of 140 ml(of THF and 9.30 g (0.0364 mole) of 
(S)-(-)-2-amino-3-methyl-1,1-diphenylbutanol was cooled to -78.degree. C. 
and 2.90 g of borane.dimethyl sulfide complex was added thereto with 
stirring. The temperature of the mixture was then raised to room 
temperature over a period of about 3 hours. Then, 2.90 g of 
borane.dimethyl sulfide complex was further added to the mixture, which 
was then stirred for 15 minutes. 
Then, a mixture of 7 g (0.026 mole) of 2-benzyloxypropiophenone 
O-methyloxime obtained in the second paragraph in Referential Example 2 
(Table 2, No. 2) and 10 ml of THF was added, and the resulting mixture was 
stirred at room temperature for 20 hours and then at 50.degree. C. for 1 
hour. 
Then, the reaction liquid was treated according to the same procedures as 
in Referential Example (3-1) involving addition of 10% hydrochloric acid, 
concentration under reduced pressure, neutralization with alkali, 
extraction with chloroform and purification by column chromatography, to 
obtain 4.5 g of (+)-1-(2benzyloxyphenyl)propylamine; which had an oily 
appearance and an optical purity of 49.6%. 
.sup.1 H-NMR spectrum [.delta.ppm, CDCl.sub.3 ]; 
0.89 (3H, t), 1.58 (2H, s), 1.67-1.98 (2H, q), 
4.12 (H, t), 5.08 (2H, s), 6.8-7.35 (4H, m), 
7.39 (5H, s). 
In 170 ml of water was dissolved 5.17 g of the hydrochloride of the above 
amine, and a solution consisting of 3.23 g of N-acetyl-L-leucine and 18.6 
ml of 1 N NaOH solution was added. Collecting the precipitated crystals by 
filtration gave 3.40 g of N-acetyl-L-leucine salt of 
(+)-1-(2-benzyloxyphenyl)-propylamine, having an [.alpha.].sub.D.sup.20 of 
+12.1.degree. (C. 0.5, water). 
Then, the salt obtained above was added to aqueous sodium hydroxide 
solution to form free amine, which was then extracted with chloroform to 
obtain 1.95 g of (+)-1-(2-benzyloxyphenyl)propylamine as an oil, having an 
optical purity of 97.0% and an [.alpha.].sub.D.sup.20 of 14.86.degree. (C. 
1.0, water) (hydrochloride). 
(3-3) (-)-1-(2-Benzyloxy-3-methylphenyl)ethylamine 
A mixture of 15.83 g (0.062 mole) of 
(S)-2-amino-3-methyl-1,1-diphenylbutanol and 260 ml of 1,2-dichloroethane 
was cooled to -30.degree. C., 4.95 g of borane.dimethyl sulfide complex 
was added thereto, and the temperature of the mixture was elevated to 
10.degree. C over a period of 2 hours. Then, 4.95 g of borane.dimethyl 
sulfide complex was further added thereto, and the temperature was raised 
to room temperature over a period of 1 hour. 
Then, a mixture of 11.93 g (0.0443 mole) of 
2-benzyloxy-3-methylacetophenone O-methyloxime obtained in the second 
paragraph in Referential Example 2 (Table 2, No. 3) and 15 ml of 
1,2-dichloroethane was added, the resulting mixture was stirred at room 
temperature for 21 hours and then at 50.degree. C. for 1 hour, and then 
120 ml of 10% hydrochloric acid was added thereto. 
The thus precipitated (S)-(-)-2-amino-3-methyl-1,1-diphenylbutanol 
hydrochloride was filtered off. The filtrate was made alkaline with 
aqueous sodium hydroxide solution, and the organic layer was separated and 
concentrated under reduced pressure. 
The concentrate was then purified by silica gel column chromatography with 
ethyl acetate used as eluting solvent to remove the ligand and other 
impurities contained in a small amount. Thus, 5.2 g of 
(-)-1-(2-benzyloxy-3-methylphenyl)ethylamine was obtained, having an 
[.alpha.].sub.D.sup.20 of -4.8.degree. (C. 1.4, methanol) and an optical 
purity of 79.8%. .sup.1 H-NMR spectrum [.delta.ppm, CDCl.sub.3 ; 
1.36 (3H, d), 1.62 (2H, s), 2.35 (3H, s), 
4.47 (H, q), 4.85 (2H, s), 7.0-7.6 (8H, m). 
(3-4) (-)-1-(2-Benzyloxy-3-methoxyphenyl)ethylamine 
Reactions and purifications were carried out in the same manner as in 
Referential Example (3-3) except that 8.56 g (0.03 mole) of 
2-benzyloxy-3-methoxyacetophenone O-methyloxime obtained in Referential 
Example 2 (Table 2, No. 4) was used as the oxime ether compound, to obtain 
5.0 g of (-)-1-(2-benzyloxy-3-methoxyphenyl)ethylamine having an optical 
purity of 73.6% and an [.alpha.].sub.D.sup.20 of -28.1.degree. (C. 1.0, 
water)(hydrochloride). 
The hydrochloride of the above amine was dissolved in 20 ml of water and 
added to a solution consisting of 3.36 g of N-acetyl-L-leucine and 19.1 ml 
of aqueous 1N sodium hydroxide solution. 
The precipitated crystals were collected by filtration, converted to free 
amine by use of aqueous sodium hydroxide solution and then extracted with 
methylene chloride. Thus, 3.17 g of 
(-)-1-(2-benzyloxy-3-methoxyphenyl)ethylamine was obtained; which had an 
optical purity of 95.0% and an [.alpha.].sub.D.sup.24 of -35.66.degree. 
(C. 0.99, water) (hydrochloride). .sup.1 H-NMR spectrum [.delta.ppm, 
CDCl.sub.3 ]; 
1.29 (3H, d), 2.63 (2H, s), 3.88 (3H, s), 
4.83 (1H, q), 5.04 (2H, s), 6.8-7.17 (3H, m), 
7.2-7.55 (5H, m). 
(3-5) (+)-1-(2-Benzyloxy-5-methoxyphenyl)ethylamine 
Reactions and purifications were carried out in the same manner as in 
Referential Example (3-3) except that 7.42 g (0.026 mole) of 
2-benzyloxy-5-methoxyacetophenone O-methyloxime obtained in Referential 
Example 2 (Table 2, No. 5) was used as the oxime ether compound. Thus, 
3.76 g of (+)-1-(2-benzyloxy-5-methoxyphenyl)ethylamine was obtained. The 
hydrochloride thereof showed an optical rotation [.alpha.].sub.D.sup.26 of 
+2.45.degree. (C. 0.94, water). Recrystallization from isopropanol yielded 
2.68 g of purified product having an optical purity of 95.2% and an 
[.alpha.].sub.D.sup.24 of +3.41.degree. (C. 1.0, water) (hydrochloride). 
.sup.1 H-NMR spectrum [.delta.ppm, CDCl.sub.3 ]; 
1.39 (3H, d), 1.69 (2H, s), 3.77 (3H, s), 
4.42 (2H, q), 5.04 (2H, s), 6.6-7.0 (3H, m), 
7.2-7.5 (5H, m). 
(3-6) (-)-1-(3-Benzyloxyphenyl)ethylamine 
Reactions and purifications were carried out in the same manner as in 
Referential Example (3-3) except that 6.64 g of 3-benzyloxyacetophenone 
O-methyloxime obtained in Referential Example (2-6) was used as the oxime 
ether compound, to obtain (-)-(3-benzyloxyphenyl)ethylamine; which had an 
optical purity of 87.4% and an [.alpha.].sub.D.sup.26 of -2.56.degree. (C. 
1.05, water) (hydrochloride). 
(3-7) (-) and (+)-1-(2-Benzyloxyphenyl)ethylamine 
To a solution consisting of 56.26 g (0.22 mole) of 2-benzyloxyacetophenone 
O-methyloxime obtained in the same manner as in Referential Example 2 
(Table 2, No. 1) and 250 ml of THF, was added 26.74 g (0.352 mole) of 
borane.dimethyl sulfide complex at room temperature. The resulting mixture 
was stirred for 5 hours and then allowed to stand overnight. 
Then, 10% hydrochloric acid solution was added to the reaction mass to 
decompose the reducing agent. The reaction mixture was then made alkaline 
by addition of aqueous sodium hydroxide solution, extracted with methylene 
chloride, washed with water, dried, concentrated and distilled to obtain 
48.6 g of (.+-.)-1-(2-benzyloxyphenyl)ethylamine, having a b.p. 
152.degree.-153.degree. C./18 mmHg. 
The above amine was made into its hydrochloride with hydrochloric acid. To 
a solution consisting of 1.319 g (5 mmoles) of the hydrochloride and 14 ml 
of water, were added at room temperature 0.761 g (5 mmoles) of 
(+)-mandelic acid, 1 ml of water and 5 ml of aqueous 1N sodium hydroxide 
solution, whereby crystals were precipitated. After addition of 5 ml of 
water followed by recrystallization, 0.93 g of the (+)-mandelic acid salt 
([.alpha.].sub.D.sup.24 .+-.36.3.degree. (C. 0.97, water)) of crude 
(-)-1-(2-benzyloxyphenyl)ethylamine was obtained. It was then 
recrystallized from water to give 0.53 g of purified salt 
([.alpha.].sub.D.sup.24 +32.05.degree. (C. 0.82, water)). The salt was 
decomposed with aqueous sodium hydroxide solution and extracted with 
chloroform to give 0.31 g of (-)-1-(2-benzyloxyphenyl)ethylamine 
([.alpha.].sub.D.sup.24 -19.1.degree. (C. 1.0, water) (hydrochloride)). 
Analysis by high performance liquid chromatography with an optically 
active column showed an optical purity of 99% or more. 
Crystals which had been precipitated from the mother liquor obtained after 
separation of said (+)mandelic acid salt of crude 
(-)-1-(2-benzyloxyphenyl)ethylamine were collected by filtration and dried 
to give 0.31 g of (+)-mandelic acid salt of 
(+)-(2-benyloxyphenyl)ethylamine; [.alpha.].sub.D.sup.25 59.35.degree. (C. 
0.83, water). 
The above salt was decomposed with aqueous sodium hydroxide solution and 
extracted with chloroform to give 0.18 g of 
(+)-1-(2-benzyloxyphenyl)ethylamine ([.alpha.].sub.D.sup.25 +19.27.degree. 
(C. 1.1, water) (hydrochloride)); optical purity: 98.2%, m.p.: 
154.degree.-156.degree. C. (hydrochloride). 
EXAMPLE 1 
A mixture obtained by adding 2.64 g of (+)-1-(2-benzyloxyphenyl)ethylamine 
hydrochloride prepared in Referential Example (3-1) and 0.26 g of 5% Pd-C 
to 40 ml of methanol was subjected to hydrogenation at room temperature 
and normal pressure, whereby 256 ml of hydrogen was absorbed. After 
filtering off the catalyst, the filtrate was concentrated under reduced 
pressure to give 1.78 g of (+)-1-(2-hydroxyphenyl)ethylamine 
hydrochloride. 
[.alpha.].sub.D.sup.17 +21.36.degree. (C. 1.06, water), m.p.: 
135.degree.-136.degree. C. 
The above salt was neutralized with aqueous ammonia solution and extracted 
with methylene chloride to give 1.30 g of 
(+)-1-(2-hydroxyphenyl)ethylamine. 
[.alpha.].sub.D.sup.24 + 12.24.degree. (C. 1.1, CHCl.sub.3), m.p.: 
83.degree.-83.5.degree. C. 
NMR spectrum [.delta.ppm, CDCl.sub.3 DMF-d.sub.7) (hydrochloride) 
1.70 (3H, d), 4.70 (1H, q), 6.6-7.5 (4H, m), 
7.4-8.7 (4H, broad) 
EXAMPLE 2 
In the same manner as in Example 1 except for using 1.37 g of 
(+)-1-(2-benzyloxyphenyl)propylamine hydrochloride obtained in Referential 
Example (3-2) in place of (+)-1-(2-benzyloxyphenyl)ethylamine used in 
Example 1, 0.95 g of (+)-1-(2-hydroxyphenyl)propylamine hydrochloride was 
obtained. 
[.alpha.].sub.D.sup.21 +28.6.degree. (C. 1.2, water), m.p.: 
194.degree.-196.degree. C. 
The above salt was neutralized and treated in the same manner as in Example 
1 to obtain 0.72 g of free amine as an oily substance. 
[.alpha.].sub.D.sup.22 +17.21.degree. (C. 1.32, CHCl.sub.3) 
NMR spectrum [.delta.ppm, CDCl.sub.3 ]; 
0.89 (3H, t), 3.96 (H, t), 1.75 (2H, m), 
6.6-7.25 (4H, m), 3.5-5.5 (3H, broad) 
EXAMPLE 3 
Procedures involving reaction and neutralization were followed in the same 
manner as in Example 1 except for using 
(-)-1-(2-benzyloxy-3-methylphenyl)ethylamine hydrochloride obtained in 
Referential Example (3-3) in place of (+)-1-(2-benzyloxyphenyl)ethylamine 
used in Example 1, to obtain 1.38 g of 
(+)-1-(2-hydroxy-3-methylphenyl)ethylamine as crystals. Recrystallization 
from cyclohexane gave 1.08 g of a purified product of an optical purity of 
98.8%. 
[.alpha.].sub.D.sup.25 +17 8.degree. (C. 1.1, CHCl.sub.3), m.p.: 
115.degree..116.degree. C. 
NMR spectrum [.delta.ppm, CDCl.sub.3 -DMF-d.sub.7 ] (hydrochloride) 
1.68 (3H, d), 4.80 (1H, q), 2.29 (3H, s), 
6.68-7.40 (3H, m), 7.8-9.0 (4H, broad) 
EXAMPLE 4 
Procedures involving reaction and neutralization were followed in the same 
manner as in Example 1 except for using 3.21 g of 
(-)-1-(2-benzyloxy-3-methoxyphenyl)ethylamine hydrochloride obtained in 
Referential Example (3-4) in place of (+)-1-(2-benzyloxyphenyl)ethylamine 
used in Example 1, to obtain 1.81 g of crystals of 
[.alpha.].sub.D .sup.24 +13.14.degree. (C. 1.04, ethyl acetate), 
m p.: 95.degree.-97.degree. C. 
NMR spectrum [.delta.ppm, CDCl.sub.3 ]; 
1.46 (3H, d), 3.86 (3H, s), 4.35 (1H, q), 
4.4-5.0 (3H, broad) 
EXAMPLE 5 
Procedures involving reaction and neutralization were followed in the same 
manner as in Example 1 except for using 2.57 g of 
(+)-1-(2-benzyloxy-5-methoxyphenyl)ethylamine hydrochloride obtained in 
Referential Example (3-5) in place of (+)-1-(2-benzyloxyphenyl)ethylamine 
used in Example 1, to obtain 1.42 g of 
(+)-1-(2-hydroxy-5-methoxyphenyl)ethylamine as an oily substance. 
[.alpha.].sub.D.sup.22 +21.70.degree. (C. 0.96, chloroform) 
EXAMPLE 6 
Reaction was carried out in the same manner as in Example 1 except for 
using 3.21 g of (-)-1-(3-benzyloxyphenyl)ethylamine hydrochloride obtained 
in Referential Example (3-6) in place of 
(+)-1-(2-benzyloxyphenyl)ethylamine hydrochloride used in Example 1. 
After catalyst removal by filtration, concentration under reduced pressure, 
neutralization with ammonia and extraction with ethyl acetate, 1.60 g of 
(-)-1-(3-hydroxyphenyl)ethylamine was obtained. 
[.alpha.].sub.D.sup.24 - 24.52.degree. (C. 0.98, ethyl acetate) 
NMR spectrum (67ppm, CDCl.sub.3); 
1.40 (3H, d), 3.0-3.4 (3H, s), 4.09 (1H, q), 
6.6-6.9 (3H, m), 7.08-7.2 (1H) 
EXAMPLE 7 
In a nitrogen atmosphere, 0.10 ml (1 mmole) of borane.dimethyl sulfide 
complex was added to a a solution consisting of 0.1372 g (1 mmole) of 
(+)-1-(2-hydroxyphenyl)ethylamine and 4 ml of deuterochloroform at 
0.degree. C, and the mixture was stirred at the temperature for 1 hour and 
then at room temperature for 0.5 hour. 
Then, 0.10 ml (1 mmole) of borane.dimethyl sulfide complex was further 
added thereto and stirred at room temperature for 0.75 hour. Thus, an 
optically active amine-boron compound was prepared. 
The .sup.11 B-NMR spectrum of the compound was determined as follows: 
[.delta.ppm, reference: BF.sub.3.OEt.sub.2 ]; 
-37.1, -20.2, +1.3, +2.5, +21.0, +26.1 
EXAMPLES 8 to 10 
Optically active amine-boron compounds were prepared in the same manner as 
in Example 7 but by using (+)-1-(2-hydroxy-3-methoxyphenyl)ethylamine, 
(+)-1-(2-hydroxy-3-methylphenyl)ethylamine and 
(+)-1(2-hydroxy-5-methoxyphenyl)ethylamine, respectively, in place of 
(+)-1-(2-hydroxyphenyl)ethylamine used in Example 7. The results of 
determination of .sup.11 B-NMR of the compounds obtained are shown in 
Table 1. 
TABLE 1 
______________________________________ 
.sup.11 B-NMR spectrum 
Example No. [.delta. ppm, reference: BF.sub.3.OEt.sub.2 ] 
______________________________________ 
8 -39.0, -20.3, +1.0, +21.0, +27.2 
9 -20.4, -5.0, +0.5, +1.5, +20.8, +26.9 
10 -20.4, +1.3, +2.3, +20.8, +26.7 
______________________________________ 
EXAMPLE 11 
A mixture of 0.9 mmole (0.124 g) of (+)-1(2-hydroxyphenyl)ethylamine 
obtained in Example 1 and 2.5 ml of THF was cooled to -78.degree. C., 0.9 
mmole (1.15 ml) of 0.78 M borane.THF solution was added thereto, and the 
mixture was brought up to room temperature with stirring over a period of 
2 hours. Then, 0.9 mmole of 0.78 M borane.THF solution was further added 
thereto, followed by stirring for 30 minutes. 
Then, at room temperature, a solution consisting of 0.6 mmole (0.153 g) of 
2-benzyloxyacetophenone O-methyloxime (anti/syn =88/12) and 2 ml of THF 
was added thereto, and the resulting mixture was stirred at room 
temperature for 24 hours and then at 45.degree. C. for 1.5 hours. 
Then, 4 ml of 10% hydrochloric acid was added to the reaction mass, which 
was then concentrated under reduced pressure, mixed with diethyl ether and 
water, and separated into layers. The aqueous layer was made alkaline with 
aqueous sodium hydroxide solution and extracted with chloroform to obtain 
0.12 g of (-)-1-(2-benzyloxyphenyl)ethylamine in 88% yield. The optical 
yield was 50%. 
The aqueous layer which remained after said extraction with chloroform was 
acidified with hydrochloric acid, then neutralized with ammonia and 
extracted with chloroform, whereby 0.10 g of 
(+)-1-(2-hydroxyphenyl)ethylamine was recovered as crystals. The optical 
purity was found to be 87.2%, the same as that before use. 
EXAMPLES 12 to 18 AND COMATIVE EXAMPLE 1 
According to the procedures of Example 11, a series of asymmetric reduction 
of acetophenone O-methyloxime (anti/syn =97/3) was carried out by using 
various optically active benzylamines obtained in Examples 1 to 6 and 
(-)-1-(4-hydroxyphenyl)ethylamine as the asymmetric ligand, to obtain 
(+)-.alpha.-phenethylamine. The results obtained are shown in Table 3. 
TABLE 3 
______________________________________ 
Asymmetric Boron Optical 
ligand*.sup.1 hydride Reaction yield*.sup.2 
R.sub.1 R.sub.2 
compound solvent (%) 
______________________________________ 
Example 
12 H CH.sub.3 
BH.sub.3.THF 
THF 66 
13 " " BH.sub.3.S(CH.sub.3).sub.2 
1,2- 74 
Dichloro- 
ethane 
14 " C.sub.2 H.sub.5 
" 1,2- 71 
Dichloro- 
ethane 
15 3-CH.sub.3 
CH.sub.3 
" 1,2- 78 
Dichloro- 
ethane 
16 3-OCH.sub.3 
" " 1,2- 84 
Dichloro- 
ethane 
17 5-OCH.sub.3 
" " 1,2- 73 
Dichloro- 
ethane 
18 (-)-1-(3- " THF 26 
Hydroxy- 
phenyl)- 
ethylamine 
Com- (-)-1-(4- " " 11 
parative 
Hydroxy- 
Example phenyl)- 
1 ethylamine 
______________________________________ 
Note: 
##STR9## 
*.sup.2 (+).alpha.-Phenethylamine 
EXAMPLES 19 to 29 
Reactions were carried out in the same manner as in Example 11 except for 
using the various substrates shown in Table 4 in place of 
2-benzyloxyacetophenone O-methyloxime used in Example 11. The results thus 
obtained are shown in Table 4. 
EXAMPLE 30 
Reaction was carried out in the same manner as in Example 11 except for 
using (-)-1-(3-hydroxyphenyl)ethylamine in place of 
(+)-1-(2-hydroxyphenyl)ethylamine and using phenyl p-tolylmethyl ketone 
O-methyloxime in place of 2-benzyloxyacetophenone O-methyloxime. The 
results obtained are shown in Table 4. 
COMATIVE EXAMPLE 2 
In the same manner as in Example 31 except for using 
(-)-1-(4-hydroxyphenyl)ethylamine was used in place of 
(-)-1-(3-hydroxyphenyl)ethylamine used in Example 30. The results obtained 
are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Boron Optical 
hydride 
Reaction yield 
Substrate compound 
solvent 
Product (%) 
__________________________________________________________________________ 
Example 
19 
2-Methoxyacetophenone 
BH.sub.3.THF 
THF (-)-1-(2-Methoxyphenyl)- 
67 
O-methyloxime (anti) ethylamine 
20 
2-Isopropoxyacetophenone 
" " (-)-1-(2-Isopropoxy- 
49 
O-methyloxime phenyl)ethylamine 
(anti/syn = 87/13) 
21 
4-Bromoacetophenone 
BH.sub.3.SMe.sub.2 
" (-)-1-(4-Bromophenyl)- 
69 
O-methyloxime ethylamine 
(anit/syn = 97/3) 
22 
1-Acenaphthone 
" 1,2-Dichloro- 
(-)-1-(1-Naphthyl)- 
67 
O-methyloxime (syn) 
ethane ethylamine 
23 
1-Acenaphthone 
" 1,2-Dichloro- 
(+)-1-(1-Naphthyl)- 
68 
O-methyloxime (anti) 
ethane ethylamine 
24 
2-Octanone " 1,2-Dichloro- 
(-)-1-Methylheptylamine 
74 
O-benzyloxime (anti) 
ethane 
25 
Cyclohexyl benzyl ketone 
" 1,2-Dichloro- 
(-)-1-Cyclohexyl-2- 
80 
O-methyloxime (syn) 
ethane phenylethylamine 
26 
Phenyl p-tolylmethyl 
" 1,2-Dichloro- 
(1)-1-Phenyl-2-(p-tolyl)- 
71 
ketone O-n-octyloxime 
ethane ethylamine 
(anti) 
27 
Phenyl p-tolylmethyl 
" 1,2-Dichloro- 
(-)-1-Phenyl-2-(p-tolyl)- 
69 
ketone O-trimethyl- 
ethane ethylamine 
silyloxime (anti) 
28 
Phenyl p-tolylmethyl 
" 1,2-Dichloro- 
(+)-1-Phenyl-2-(p-tolyl)- 
76 
ketone O-methyloxime 
ethane ethylamine 
(syn) 
29 
Phenyl p-tolylmethyl 
" 1,2-Dichloro- 
(-)-1-Phenyl-2-(p-tolyl)- 
77 
ketone O-methyloxime 
ethane ethylamine 
(anti) 
30 
Phenyl p-tolylmethyl 
" THF (-)-1-Phenyl-2-(p-tolyl)- 
19 
ketone O-methyloxime ethylamine 
(anti) 
Comparative 
Phenyl p-tolylmethyl 
" " (-)-1-Phenyl-2-(p-tolyl)- 
1 
Example 2 
ketone O-methyloxime ethylamine 
(anti) 
__________________________________________________________________________ 
EXAMPLE 31 
In a nitrogen atmosphere, 3.75 mmole (0.375 ml) of borane.dimethyl sulfide 
complex was added at -30.degree. C. to a solution consisting of 1.5 mmoles 
(0.206 g) of (+)-1-(2-hydroxyphenyl)ethylamine and 4 ml of THF, and the 
resulting mixture was brought up to room temperature over a period of 2 
hours. 
Then, a solution consisting of 1 mmole (0.12 g) of acetophenone and 1 ml of 
THF was added to the mixture and stirred for 24 hours. 
Thereafter, 3 ml of 10% hydrochloric acid was added thereto, the resulting 
mixture was stirred at 50.degree. C. for 1 hour and then extracted with 
chloroform. The extract was washed with 10% hydrochloric acid and then 
with water, and dried to obtain (-)-1-phenylethanol in 100% conversion. 
The above product was converted into the urethane derivative and analyzed 
for its isomer ratio by high performance liquid chromatography with an 
optically active column and the optical yield was determined. The results 
obtained are shown in Table 5. 
EXAMPLES 32 to 34 
The procedures in Example 31 were repeated except that n-propyl phenyl 
ketone, isopropyl phenyl ketone and methyl n-hexyl ketone were used 
respectively in place of acetophenone used in Example 31. The results 
obtained are shown in Table 5. 
EXAMPLE 35 
The procedures in Example 31 were repeated except that 
(-)-1-(3-hydroxyphenyl)ethylamine was used in place of 
(+)-1-(2-hydroxyphenyl)ethylamine used in Example 31. The results obtained 
are shown in Table 5. 
Comparative Example 3 
The procedures in Example 31 were repeated except that 
(+)-.alpha.-phenylethylamine was used in place of 
(+)-1-(2-hydroxyphenyl)ethylamine used in Example 31. The results obtained 
are shown in Table 5. 
TABLE 5 
______________________________________ 
Optical 
Substrate Product yield(%) 
______________________________________ 
Example 
31 Acetophenone 
(-)-1-Phenylethanol 
23 
32 n-Propyl phenyl 
(-)-1-Phenylbutanol 
24 
ketone 
33 i-Propyl phenyl 
(-)-1-Phenyl-2- 
19 
ketone methylpropanol 
34 Methyl n-hexyl 
(+)-2-Octanol 
17 
ketone 
35 Acetophenone 
(-)-1-Phenylethanol 
11 
Comparative 
" " 1 
Example 3 
______________________________________ 
EXAMPLES 36 TO 42 
The procedures in Example 31 were repeated except that 1-substituted 
2-triazol-1-yl-4,4-dimethyl-1-penten-3-one having various substituents 
were used respectively in place of acetophenone used in Example 31. The 
results obtained are shown in Table 6. 
EXAMPLE 43 
The procedures in Example 31 were repeated except that 
1-(2,4-dichlorophenyl)-2-triazol-1-yl-4,4-dimethyl1-penten-3-one was used 
in place of acetophenone and (-)-1(3-hydroxyphenyl)ethylamine was used in 
place of (+)-(2-hydroxyphenyl)ethylamine. The results obtained are shown 
in Table 6. 
COMATIVE EXAMPLES 4 AND 5 
The procedures in Example 43 were repeated except that 
(-)-1(4-hydroxyphenyl)ethylamine and (+)-.alpha.-phenylethylamine were 
used respectively in place of (-)-1(3-hydroxyphenyl)ethylamine used in 
Example 43. The results obtained are shown in Table 6. 
TABLE 6 
__________________________________________________________________________ 
##STR10## 
Substrate 
Boron Product 
(E-form/ 
hydride 
E-form/ 
Optical* 
Optical* 
R Z-form) 
compound 
Z-form 
rotation 
yield (%) 
__________________________________________________________________________ 
Example 
36 
##STR11## 
95/5 BH.sub.3.SMe.sub.2 
92.2/7.8 
(-) 59 
37 
##STR12## 
100/0 BH.sub.3.THF 
99.3/0.7 
(+) 77** 
38 
##STR13## 
88.1/11.9 
BH.sub.3.SMe.sub.2 
85.9/14.1 
(+) 50 
39 
##STR14## 
99.9/0.1 
" 97.2/2.8 
(+) 50 
40 
##STR15## 
99.9/0.1 
" 97.9/2.1 
(-) 38 
41 
##STR16## 
100/0 " 99.9/0.1 
(-) 58 
42 
##STR17## 
99.8/0.2 
BH.sub.3.THF 
99.0/1.0 
(+) 73** 
43 
##STR18## 
99.8/0.2 
BH.sub.3.SMe.sub.2 
99.6/0.4 
(+) 16 
Comparative 
4 
" " BH.sub.3.THF 
97.4/2.6 
(+) 4 
Example 
5 
" " " 97.5/2.5 
(+) 8 
__________________________________________________________________________ 
Note: 
*E-form alcohol 
**3.5 Equivalents of BH.sub.3.THF was used relative to the ligand.