Chiral amido-phosphine-phosphinite compounds

Details Chiral amido-phosphine-phosphinite compounds Chiral amido-phosphine-phosphinite compounds

1998-03-05

2002-02-19

Vollano, Jean F. (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Phosphorus esters

C558S155000, C564S012000, C549S491000

Reexamination Certificate

active

06348612

ABSTRACT:

BACKGROUND OF THE INVENTION
Enantiomerically pure (R) or (S) compounds can be produced by causing compounds to undergo enantioselective reactions. Use of enantioselective catalysts which are capable of catalyzing asymmetric hydrogenations, enantioselective hydrogen displacements and allylic substitution reactions, among others, can facilitate the attainment of high optical yields. The present invention relates to novel chiral amidophosphine-phosphinite compounds and complexes of these compounds as ligands with Group VIII metals, which complexes may be used as enantioselective catalysts.
SUMMARY OF THE INVENTION
The present invention is concerned with novel chiral, amido-phosphine-phosphinite compounds, which are present in (R) or (S) form, of formula (I)
wherein
R
1
signifies C
2-8
-alkyl, C
3-8
-cycloalkyl or aryl-C
1-4
-alkyl,
R
2
signifies C
1-8
-alkyl, C
3-8
-cycloalkyl, aryl-C
1-4
-alkyl or aryl and
R
3
and R
4
each independently signify C
1-8
-alkyl, C
3-8
-cycloalkyl, aryl-C
1-4
-alkyl, aryl or heteroaryl or R
3
and R
4
together with the respective phosphorus atom signify a 9-dibenzophospholyl, 9-phosphabicyclo[3.3.1]nonyl or 9-phosphabicyclo[4.2.1]nonyl group and
* denotes a chiral center.
The invention is also concerned with the manufacture of the amidophosphine-phosphinite compounds of formula I, complexes of these compounds as ligands with Group VIII metals and optionally with additional ligands as well as the use of the complexes as catalysts for enantioselective reactions such as e.g. asymmetric hydrogenations, enantioselective hydrogen displacements, allylic substitution reactions and the like.
The object of the present invention is to provide novel, chiral amidophosphine-phosphinite compounds which can be used in the form of the aforementioned complexes in enantioselective reactions and thereby facilitate high optical yields. The object is achieved by the chiral amidophosphine-phosphinite compounds of formula I.
DETAILED DESCRIPTION OF THE INVENTION
The following definitions of the general terms are used in the present specification and apply irrespective of whether the terms appear as such or in combination.
The term “C
1-4
-alkyl”, “C
1-8
-alkyl” or “C
2-8
-alkyl” signifies in the scope of the present invention a straight-chain or branched alkyl group with up to 4 or 8 carbon atoms such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert. butyl, pentyl, isopentyl, neopentyl, hexyl, tert. hexyl, heptyl, isoheptyl, octyl or isooctyl.
The term “C
3-8
-cycloalkyl” embraces cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
The term “aryl”, alone or as part of “aryl-C
1-4
-alkyl”, signifies a phenyl or naphthyl group which in each case can be either unsubstituted or mono- or multiply-substituted. Substituents which come into consideration here are halogen, C
1-8
-alkyl and C
1-8
-alkoxy groups, halogenated C
1-8
-alkyl and C
1-8
-alkoxy groups, di(C
1-8
-alkyl)amino, tri(C
1-4
-alkyl)silyl (preferably trimethylsilyl) and phenyl, whereby several substituents present can be the same or different. In the case of “aryl-C
1-4
-alkyl” this preferably signifies unsubstituted benzyl.
The term “halogen” signifies fluorine, chlorine, bromine or iodine.
The term “heteroaryl” signifies a 5- or 6-membered heterocyclic group having aromatic character, which has in the ring one or more hetero atoms from the group of nitrogen, oxygen and sulfur. Examples of 5-membered heterocyclic groups are pyrrolyl, thienyl and furyl, with pyridyl being an example of a 6-membered heterocyclic group. Moreover, the heterocyclic groups can be substituted in the same manner as the aryls set forth above and/or can have a fused benzene ring. Preferably, heteroaryl has no substituents.
The term “C
1-8
-alkoxy” signifies a straight-chain or branched alkoxy group with up to 8 carbon atoms, preferably with up to 4 carbon atoms.
Methoxy, ethoxy, propoxy, isopropoxy and butoxy are examples.
The term “halogenated C
1-8
-alkyl” or “halogenated C
1-8
-alkoxy” signifies an alkyl or alkoxy group which in each case is substituted with one or more halogen atoms, especially chlorine or fluorine. Examples are trifluoromethyl, trichloromethyl and pentafluoromethyl and, respectively, fluoromethoxy and chloromethoxy.
Amidophosphine-phosphinite compounds of formula I are preferred in which independently of one another R
1
signifies tert. butyl, R
2
signifies methyl and R
3
and R
4
each signify cyclohexyl, phenyl, 3-5-xylyl, 3,5-di(trifluoromethyl)phenyl, 3,5-di(tert. butyl)phenyl, 3,5-di(tert. butyl)-4-methoxyphenyl or 2-furyl or R
3
and R
4
together with the phosphorus atom signify 9-dibenzophospholyl.
Preferably, R
3
and R
4
have the same significance.
Amidophosphine-phosphinite compounds of formula I in which R
3
and R
4
signify 3,5-di(tert. butyl)phenyl are especially preferred.
Particularly preferred amidophosphine-phosphinite compounds of formula I are:
(S)- or (R)-N-(Diphenylphosphanyl)-2-[(diphenylphosphanyl)oxy]-3,3,N-trimethyl-butyramide,
(S)- or (R)-N-(dicyclohexylphosphanyl)-2-[(dicyclohexylphosphanyl)-oxy]3,3,N-trimethyl-butyramide,
(S)- or (R)-N-[di-(2-furyl)-phosphanyl]-2-[(di-(2-furyl)-phosphanyl)oxy]-3,3,N-trimethyl-butyramide,
(S)- or (R)-N-(5H-dibenzophospholyl)-2-[(5H-dibenzophospholyl)oxy]-3,3,N-trimethyl-butyramide,
(S)- or (R)-N-[bis(3,5-dimethylphenyl)-phosphanyl]-2-[(bis(3,5-dimethylphenyl)-phosphanyl)oxy]-3,3,N-trimethyl-butyramide,
(S)- or (R)-N-[bis(3,5-di(trifluoromethyl)phenyl)-phosphanyl]-2-[(bis(3,5di(trifluoromethyl)phenyl)-phosphanyl)oxy]-3,3,N-trimethyl-butyramide,
(S)- or (R)-N-[bis(3,5-di(tert. butyl)phenyl)-phosphanyl]-2-[(bis(3,5-di-(tert. butyl)phenyl)-phosphanyl)oxy]-3,3,N-trimethyl-butyramide and
(S)- or (R)-N-[bis(3,5-di(tert. butyl)-4-methoxyphenyl)-phosphanyl]-2-[(bis(3,5-di(tert. butyl)-4-methoxyphenyl)-phosphanyl)oxy]-3,3,N-trimethyl-butyramide.
The amidophosphine-phosphinite compounds of formula I in accordance with the invention (in the role of ligands) form complexes with transition metals of Group VIII, especially with rhodium, iridium, ruthenium and palladium, and such complexes are likewise an object of the present invention; they can be used as catalysts for enantioselective reactions, especially for Aasymmetric hydrogenations, enantioselective hydrogen displacements and allylic substitution reactions.
These complexes in accordance with the invention of the compounds of formula I with transition metals of Group VIII can contain further ligands. Examples of such complexes, which are likewise in accordance with the invention, are especially optically active cationic and neutral rhodium, iridium, ruthenium and palladium complexes of formulas
[Rh(Y)(L)
n
]
+
A
−
II-a
[Rh(Y)(L)
n
B]
II-b
[Ir(Y)(L)
n
]
+
A
−
II-c
[Ir(Y)(L)
n
B]
II-d
[Ir(Y)(B)
4
]
−
r
M
r+
II-e
[IrH(Y)(B)
2
]
II-f
[Ir(Y)(B)
3
]
2
II-g
[Ir(B)
3
(Y)]
II-h
[Ru(Y)]
2+
(A
−
)
2
II-i
[Ru(Y)(B)
2
]
II-j
[Ru(Y)(C
1
)(C
2
)
2−m
](C
3
)
m
II-k
[Pd(Y)(B)
2
]
II-1
[Pd(Y)
2
]
II-m
[Pd(Y)(L)
n
]
2+
(A
−
)
2
II-n
wherein
L signifies a neutral ligand,
A
−
signifies an anion of an oxygen acid or complex acid,
B signifies an anionic coordinating ligand,
C
1
signifles benzene, p-cymene, xylene or hexamethylbenzene,
C
2
signifies halogen,
C
3
signifies halogen or A
−
,
n signifies 0, 1 or 2,
m signifies 0, 1 or 2,
r signifies 1 or 2,
M
r+
signifies an alkali metal or alkaline earth ion or a tetra-substituted ammonium ion (r is 1,2 or, respectively, 1) from the group of (C
1-8
-alkyl)
4
N
+
,(phenyl)N
+
(C
1-8
-alkyl)
3
, (benzyl)N
+
(C
1-8
-alkyl)
3
, and
Y signifies a chiral amidophosphine-phosphinite compound of formula I.
The term “neutral ligand” (L) signifies an exch

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