Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2001-01-23
2003-12-30
Davis, Brian (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C568S704000, C568S716000, C556S110000, C564S273000, C564S274000
Reexamination Certificate
active
06670500
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a chiral copper complex, the production process thereof using chiral salicylidene ligands and asymmetric synthesis of cyclopropane-carboxylic acid compound using the complex as a catalyst.
BACKGROUND OF THE INVENTION
As a process for producing an optically active cyclopropanecarboxylic acid ester derivative, there have been known a process of reacting an olefin with a diazoacetic acid ester in the presence of a certain salicylideneaminoalcohol copper complex catalyst (JP-A 59-225194).
SUMMARY OF THE INVENTION
According to the present invention, an industrially suitable chiral copper complex comprising an optically active salicylidenaminoalcohol compound can be readily produced. Said complex is more stable to an oxide that can be contained in a cyclopropanation reaction system, reducing adverse effects of such an oxide and said salicylidenaminoalcohol compound can be recovered after said reaction in an improved yield.
The present invention provides:
1. an optically active salicylideneaminoalcohol compound of formula (1):
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 roup, and a cycloalkoxy group,
R
2
represents
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,
when X
1
represents a nitro, X
2
is a hydrogen atom,
when X
1
represents a chlorine atom, X
2
is a chlorine atom, and
when X
1
is a hydrogen atom, X
2
is a fluorine atom, and
the carbon atom denoted by “*” is an asymmetric carbon atom having either an S or R configuration,
2. a process for producing an optically active salicylideneaminoalcohol compound as defined above, which comprises reacting
an optically active amino alcohol of formula (2):
wherein R
1
, R
2
and “*” have the same meaning s as defined above, with a 2-hydroxybenzaldehyde derivative of formula (3):
wherein when X
1
and X
2
are the same as defined above,
3. a chiral copper complex prepared from a mono-valent or di-valent copper compound and an optically active salicylideneaminoalcohol compound (1) as defined above,
4. a method for producing a chiral copper complex of formula (1)′:
wherein R
1
and R
2
are the same or different and independently represent an alkyl group, an aralkyl group, a phenyl group, a 2-methoxyphenyl group, a 2-tert-butoxy-5-tert-butylphenyl group, or a 2-octyloxy-5-tert-butylphenyl group;
when X
1
represents a nitro group, X
2
is a hydrogen atom,
when X
1
represents a chlorine atom, X
2
is a chlorine atom, and
when X
1
represents a hydrogen atom, X
2
is a fluorine atom
the carbon atom denoted by “*” is an asymmetric carbon atom having either an S or R configuration,
which comprises contacting a di-valent copper compound, in an inert organic solvent, with a chiral salicylideneaminoalcohol compound of formula (1):
wherein R
1
, R
2
X
1
, X
2
and “*” respectively have the same meaning as defined above, and
5. a method for producing an optically active cyclopropane-carboxylic acid ester of formula (4):
wherein R
3
, R
4
, R
5
, R
6
and R
7
are as defined below,
which comprises reacting a prochiral olefin of formula (5):
wherein R
3
, R
4
, R
5
and R
6
are as defined below, with a diazoacetic acid ester of formula (6):
N
2
CHCO
2
R
7
(6)
wherein R
7
is as defined below, in the presence of a chiral copper complex as defined in item 3 or 4,
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 or a lower alkoxy group,
an 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, 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 which may be optionally substituted with a lower alkyl group, a lower alkoxy group, a phenoxy group or
a halogen atom,
a phenyl group which may be optionally substituted with a lower alkyl group, a lower alkoxy group or a phenoxy group,
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) and
a (C4-C6)cycloalkoxy group (e.g., cyclobutyloxy, cyclopentyloxy, cyclohexyloxy group).
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 a group as specified above.
The alkyl group represented by R
2
has the same meanings as defined above for the (C1-C8)alkyl group.
The cycloalkyl group, and the 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 represented by R
2
have the same meanings as defined above for R
1
.
Among the optically active salicylideneaminoalcohol compound of formula (1), R
1
and R
2
are preferably an alkyl group (e.g. lower alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group or the like), an aralkyl group (e.g., a benzyl group), an aryl group (e.g., a phenyl group, a 2-methoxyphenyl group, a 2-tert-butoxy-5-tert-butylphenyl group or a 2-octyloxy-5-tert-butylphenyl group).
Specific examples the optically active salicylideneaminoalcohol compound of formula (1) include optically active N-(3-fluorosalicyliden)-2-amino-1,1-di(2-butoxy-5-t-butylphenyl)-1-propanol, N-(3-fluorosalicyliden)-2-amino-1,1-di(2-octyloxy-5-t-butylphenyl)-1-propanol, N-(3-fluorosalicyliden)-2-amino-1,1-di(2-butoxy-5-t-butylphenyl)-3-phenyl-1-propanol, N-(3-fluorosalicyliden)-2-amino-1,1-di(2-methoxyphenyl)-1-propanol, N-(3-fluorosalicyliden)-2-amino-1,1-diphenyl-1-propanol, N-(3-fluorosalicyliden)-2-amino-1,1-di(2-benzyloxy-5-methylphenyl)-3-(4-isopropoxyphenyl)-1-propanol, N-(3-fluorosalicyliden)-2-amino-1,1-diphenyl-3-phenyl-1-propanol, N-(3-fluorosalicyliden)-2-amino-1,1-di(2-methoxyphenyl)-3-methyl-1-butanol, N-(3,5-dichlorosalicylidene)-2-amino-1,1-diphenyl-1-propanol, N-(3,5-dichlorosalicylidene)-2-amino-1,1-di-(2-methoxyphenyl)-1-propanol N-(3,5-dichlorosalicylidene)-2-amino-1,1-di(5-tert-butyl-2-tert-butoxyphenyl)-3-phenyl-1-pro
Hagiya Koji
Itagaki Makoto
Kamitamari Masashi
Suzukamo Gohfu
Yamamoto Michio
Birch & Stewart Kolasch & Birch, LLP
Davis Brian
Sumitomo Chemical Company Limited
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