Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-01-23
2002-10-22
Killos, Paul J. (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S102000, C560S118000, C560S176000, C560S101000
Reexamination Certificate
active
06469198
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a production process for asymmetric synthesis of cyclopropane-carboxylic acid compound using a chiral copper complex catalyst.
BACKGROUND OF THE INVENTION
As a process for producing an optically active cyclopropanecarboxylic acid ester derivative, there has been reported a process of using a chiral copper complex catalyst which was prepared by reacting equivalent or excess amount of cupric salt with optically active salicylideneaminoalcohol (JP-B 53-43955, JP-A 50-151842, JP-A 54-73758 and JP-A 59-225194).
However, in the disclosed processes said copper complex required purification by recrystallization or washing with methanol or the like to remove an excessive amount of copper compound.
SUMMARY OF THE INVENTION
According to the present invention, a chiral copper complex catalyst composition can be obtained in an industrially advantageously and can be used in an asymmetric cyclopropanation reaction with good reproducibility.
The present invention provides:
1. a chiral copper complex catalyst composition, which is obtained by contacting an optically active N-salicylideneaminoalcohol compound of formula (1):
with a mono-valent or di-valent copper compound in an inert solvent,
wherein R
1
represents
an alkyl group which may be substituted with a group selected from an alkoxy group, an aralkyloxy group, an aryloxy group, and cycloalkoxy group,
an aralkyl, aryl or cycloalkyl group all of which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, and a cycloalkoxy group,
R
2
represent
a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl or phenyl group which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, and a cycloalkoxy group,
X
1
and X
2
are the same or different and independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group or a cyano group, and two adjacent X
1
and X
2
together with the benzene ring to which they are bonded may form a 1-hydroxy-2- or 2-hydroxy-1-naphthyl group, and
the carbon atom denoted by “*” is an asymmetric carbon atom having either an S or R configuration, and
the amount of the mono-valent or di-valent copper compound is less than 1 mole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (1), and
2. a process for producing an optically active cyclopropane-carboxylic acid ester of formula (2):
wherein R
3
, R
4
, R
5
and R
6
are as defined below, and
R
7
represents
an alkyl group having 1 to 8 carbon atoms,
a cycloalkyl group which may be optionally substituted with a lower alkyl group,
a benzyl group or phenyl group which may be optionally substituted with a lower alkyl group, a lower alkoxy group or a phenoxy group,
which comprises the steps of:
(a) contacting an optically active N-salicylideneaminoalcohol compound of formula (1):
with a mono-valent or di-valent copper compound in an inert solvent,
wherein R
1
, R
2
, X
1
, X
2
and “*” have the same meanings as defined above, and the amount of the mono-valent or di-valent copper compound is less than 1 mole per 1 mole of the optically active N-salicylideneaminoalcohol compound of formula (1), and
(b) reacting a prochiral olefin of formula (3):
wherein R
3
, R
4
, R
5
and R
6
independently represent a hydrogen atom,
a halogen atom,
a (C1-C10)alkyl group which may be substituted with a halogen atom
or a lower alkoxy group,
a (C4-C8)cycloalkyl group,
an aryl group which may be substituted with a halogen atom, a lower
alkyl group, or a lower alkoxy group,
R
3
and R
4
, or R
5
and R
6
may be bonded at their terminals to form an
alkylene group having 2-4 carbon atoms, and
one of R
3
, R
4
, R
5
and R
6
groups represents an alkenyl group which may be substituted with a halogen atom, an alkoxy group or an alkoxy carbonyl group, of which alkoxy may be substituted with a halogen atom or atoms provided that when R
3
and R
5
are the same, R
4
and R
6
are not the same,
with a diazoacetic acid ester of formula (4):
N
2
CHCO
2
R
7
(4)
wherein R
7
is the same as defined above, in the presence of a chiral copper complex catalyst composition so produced in step (a).
DETAILED DESCRIPTION
First, a description will be made to the optically active salicylideneaminoalcohol compound of formula (1) as defined above.
Examples of the alkyl group which may be substituted with a group selected from an alkoxy group, an aralkyloxy group, an aryloxy group and a cycloalkoxy group, represented by R
1
, include
a (C1-C8)alkyl group (e.g., a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-pentyl, n-octyl, n-nonyl, or n-decyl group) which may be substituted with a group selected from
a (C1-C4)alkoxy group(e.g., a methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, sec-butoxy or t-butoxy group),
a (C7-C11)aralkyloxy group(e.g., a benzyloxy or naphthylmethyloxy group),
a (C6-C11)aryloxy group(e.g., a phenoxy or naphthoxy group),
a (C4-C6)cycloalkoxy group(e.g., a cyclobutyloxy, cyclopentyloxy or cyclohexyloxy group) and the like.
Examples of the aralkyl group, the aryl group and the cycloalkyl group, all of which may be substituted with a group selected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group and a cycloalkoxy group include
a (C7-C11)aralkyl group(e.g., a benzyl, or naphthylmethyl group),
a (C6-C10)aryl group(e.g., a phenyl, or naphthyl group),
a (C4-C6)cycloalkyl group(e.g., a cyclobutyl, cyclopentyl, or cyclohexyl group), all of which may be substituted with
the (C1-C8)alkyl, (C7-C11)aralkyloxy, (C6-C11)aryloxy and (C4-C6)cycloalkoxy group as specified above and a (C1-C8)alkoxy group(e.g, a methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, sec-butoxy, t-butoxy, n-pentoxy, n-hexyloxy, n-pentyloxy or n-octyloxy group).
The alkyl group represented by R
2
include said (C1-C8)alkyl group as above. The cycloalkyl group represented by R
2
include said (C4-C6)cycloalkyl group as above.
The aralkyl or phenyl group which may be substituted with a group elected from an alkyl group, an alkoxy group, an aralkyloxy group, an aryloxy group and a cycloalkoxy group represented by R
2
include the same meanings as defined above for the groups represented by R
1
.
The substituent group X
1
and X
2
of the salicylideneaminoalcohol compound of formula (1) will be explained below.
Examples of the halogen atom represented by X
1
and X
2
include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group include a (C1-C8) alkyl group such as a methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like.
Examples of the alkoxy group include the same (C1-C4)alkoxy group as defined above in the alkoxy group for R
1
.
In salicylideneaminoalcohol compound of formula (1), preferred are
a salicylideneaminoalcohol compound (1) in which X
1
represents a bromine atom and X
2
is a hydrogen atom or a bromine atom,
a salicylideneaminoalcohol compound (1) in which X
1
represents a nitro group and X
2
is a hydrogen atom, a methyl group or a methoxy group,
a salicylideneaminoalcohol compound (1) in which X
1
represents a chlorine atom and X
2
is a chlorine atom, and
a salicylideneaminoalcohol compound (1) in which X
1
is a hydrogen atom and X
2
is a fluorine atom.
More preferred are
a salicylideneaminoalcohol compound (1) in which X
1
represents a nitro group or a bromine atom and X
2
is a hydrogen atom,
a salicylideneaminoalcohol compound (1) in which X
1
represents a chlorine atom and X
2
is a chlorine atom, and
a salicylideneaminoalcohol compound (1) in which X
1
is a hydrogen atom and X
2
is a fluorine atom.
Among the optically active salicylideneaminoalcohol compound of formula (1), R
1
is preferably an alkyl group having 1 to 6 carbon atoms, an aralkyl, an aryl group, and R
2
is preferably an alkyl group (e.g. lower alky
Itagaki Makoto
Suzukamo Gohfu
Yamamoto Michio
Birch & Stewart Kolasch & Birch, LLP
Killos Paul J.
Reyes Hector
Sumitomo Chemical Company Limited
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