Transfer hydrogenation process

Details Transfer hydrogenation process Transfer hydrogenation process

2002-02-14

2004-02-24

Kumar, Shailendra (Department: 1621)

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

Organic compounds

Amino nitrogen containing

C564S012000, C564S397000, C564S398000, C564S428000, C564S472000

Reexamination Certificate

active

06696608

ABSTRACT:

This invention relates to catalytic transfer hydrogenation, particularly in the presence of a complexed transition metal, and to a process of making optically active compounds.
According to a first aspect of the present invention there is provided a process for the transfer hydrogenation of a substrate wherein the substrate is reacted with a hydrogen donor in the presence of a transfer hydrogenation catalyst, characterised in that the substrate has the general formula
wherein:
X represents NR
3
or (NR
4
R
5
)
+
Q
−
;
Q
−
represents a monovalent anion;
R
1
and R
2
each independently represents a hydrogen atom, an optionally substituted hydrocarbyl, a perhalogenated hydrocarbyl, an optionally substituted heterocyclyl group, a substituted carbonyl functional group, a substituted thiocarbonyl functional group or substituted imino functional group, R
1
& R
2
optionally being linked in such a way as to form an optionally substituted ring;
R
3
and R
4
represents —P(O)R
6
R
7
, —P(O)OR
8
OR
9
, —P(O)OR
8
OH, —P(O)(OH)
2
, —P(O)SR
10
SR
11
, —P(O)SR
10
SH, —P(O)(SH)
2
, —P(O)NR
12
R
13
NR
14
R
15
, —P(O)NR
12
R
13
NHR
14
, —P(O)NHR
12
NHR
14
, —P(O)NR
12
R
13
NH
2
, —P(O)NHR
12
NH
2
, —P(O)(NH
2
)
2
, —P(O)R
6
OR
8
, —P(O)R
6
OH, —P(O)R
6
SR
10
, —P(O)R
6
SH, —P(O)R
6
NR
12
R
13
, —P(O)R
6
NHR
12
, —P(O)R
6
NH
2
, —P(O)OR
8
SR
10
, —P(O)OR
8
SH, —P(O)OHSR
10
, —P(O)OHSH, —P(O)OR
8
NR
12
R
13
, —P(O)OR
8
NHR
12
, —P(O)OR
8
NH
2
, —P(O)OHNR
12
R
13
, —P(O)OHNHR
12
, —P(O)OHNH
2
, —P(O)SR
10
NR
12
R
13
, —P(O)SR
10
NHR
12
, —P(O)SR
10
NH
2
, —P(O)SHNR
12
R
13
, —P(O)SHNHR
12
, —P(O)SHNH
2
, —P(S)R
6
R
7
, —P(S)OR
8
OR
9
, —P(S)OR
8
OH, —P(S)(OH)
2
, —P(S)SR
10
SR
11
, —P(S)SR
10
SH, —P(S)(SH)
2
, —P(S)NR
12
R
13
NR
14
R
15
, —P(S)NR
12
R
13
NHR
14
, —P(S)NHR
12
NHR
14
, —P(S)NR
12
R
13
NH
2
, —P(S)NHR
12
NH
2
, —P(S)(NH
2
)
2
, —P(S)R
6
OR
8
, —P(S)R
6
OH, —P(S)R
6
SR
10
, —P(S)R
6
SH, —P(S)R
6
NR
12
R
13
, —P(S)R
6
NHR
12
, —P(S)R
6
NH
2
, —P(S)OR
8
SR
10
, —P(S)OHSR
10
, —P(S)OR
8
SH, —P(S)OHSH, —P(S)OR
8
NR
12
R
13
, —P(S)OR
8
NHR
12
, —P(S)OR
8
NH
2
, —P(S)OHNR
12
R
13
, —P(S)OHNHR
12
, —P(S)OHNH
2
, —P(S)SR
10
NR
12
R
13
, —P(S)SR
10
NHR
12
, —P(S)SR
10
NH
2
, —P(S)SHNR
12
R
13
, —P(S)SHNHR
12
, —P(S)SHNH
2
, —PR
6
R
7
, —POR
8
OR
9
, —PSR
10
SR
11
, —PNR
12
R
13
NR
14
R
15
, —PR
6
OR
8
, —PR
6
SR
10
, —PR
6
NR
12
R
13
, —POR
8
SR
10
, —POR
8
NR
12
R
13
, —PSR
10
NR
12
R
13
, —S(O)R
16
, —S(O)
2
R
17
, —COR
18
, —CO
2
R
19
, or SiR
20
R
21
R
22
;
R
5
represents a hydrogen atom, an optionally substituted hydrocarbyl, a perhalogenated hydrocarbyl, or an optionally substituted heterocyclyl group;
R
6
and R
7
independently represent an optionally substituted hydrocarbyl, a perhalogenated hydrocarbyl, an optionally substituted heterocyclyl group or —N═CR
23
R
24
where R
23
and R
24
are as defined for R
1
; and
R
8
to R
22
each independently represents an optionally substituted hydrocarbyl, a perhalogenated hydrocarbyl or an optionally substituted heterocyclyl group, one or more of R
1
& R
6
, R
2
& R
7
, R
6
& R
7
, R
6
& R
8
, R
6
& R
10
, R
6
& R
12
, R
1
& R
8
, R
2
& R
9
, R
8
& R
9
, R
8
& R
10
, R
8
& R
12
, R
1
& R
10
, R
2
& R
11
, R
10
& R
11
, R
10
& R
12
, R
1
& R
12
, R
2
& R
13
, R
12
& R
13
, R
1
& R
14
, R
2
& R
15
, R
14
& R
15
, R
12
& R
14
, R
1
& R
16
, R
1
& R
18
, R
1
& R
19
, R
1
& R
20
, R
2
& R
21
, R
20
& R
21
and R
21
& R
22
optionally being linked in such a way as to form an optionally substituted ring(s).
When X represents (NR
4
R
5
)
+
Q
−
, compounds of formula (1) are iminium salts. Iminium salts include protonated iminium salts and quaternary iminium salts. Quaternary iminium salts are represented by compounds of formula (I) in which R
5
is not hydrogen.
Anions which may be represented by Q
−
include halides, optionally substituted arylsulphonates, such as optionally substituted phenyl and naphthyl sulphonates, optionally substituted alkylsulphonates including halogenated alkylsulphonates, such as C
1-20
alkylsulphonates, optionally substituted carboxylates, such as C
1-10
alkyl and aryl carboxylates, ions derived from the polyhalogenation of boron, phosphorous or antimony, and other common inorganic ions for example perchlorate. Particular examples of anions are bromide, chloride, iodide, hydrogen sulphate, tosylate, formate, acetate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, perchlorate, trifluoromethanesulphonate and trifluoroacetate. Preferred anions include bromide, chloride, iodide, formate and trifluoroacetate, and particularly preferred anions include iodide, formate and trifluoroacetate.
Hydrocarbyl groups which may be represented by one or more of R
1
, R
2
, and R
5
to R
24
, include alkyl, alkenyl, alkynyl and aryl groups, and any combination thereof, such as aralkyl and alkaryl, for example benzyl groups.
Alkyl groups which may be represented by one or more of R
1
, R
2
, and R
5
to R
24
include linear and branched alkyl groups comprising up to 20 carbon atoms, particularly from 1 to 7 carbon atoms and preferably from 1 to 5 carbon atoms. When the alkyl groups are branched, the groups often comprise up to 10 branched chain carbon atoms, preferably up to 4 branched chain atoms. In certain embodiments, the alkyl group may be cyclic, commonly comprising from 3 to 10 carbon atoms in the largest ring and optionally featuring one or more bridging rings. Examples of alkyl groups which may be represented by R
1
, R
2
, and R
5
to R
24
include methyl, ethyl, propyl, 2-propyl, butyl, 2-butyl, t-butyl and cyclohexyl groups.
Alkenyl groups which may be represented by one or more of R
1
, R
2
, and R
5
to R
24
include C
2-20
, and preferably C
2-6
alkenyl groups. One or more carbon-carbon double bonds may be present. The alkenyl group may carry one or more substituents, particularly phenyl substituents. Examples of alkenyl groups include vinyl, styryl and indenyl groups. When either of R
1
or R
2
represents an alkenyl group, a carbon-carbon double bond is preferably located at the position &bgr; to the C═X moiety. When either of R
1
or R
2
represents an alkenyl group, the compound of formula (1) is preferably an &agr;,&bgr;-unsaturated iminium compound.
Alkynyl groups which may be represented by one or more of R
1
, R
2
, and R
5
to R
24
include C
2-20
, and preferably C
2-10
alkynyl groups. One or more carbon-carbon triple bonds may be present. The alkynyl group may carry one or more substituents, particularly phenyl substituents. Examples of alkynyl groups include ethynyl, propyl and phenylethynyl groups. When either of R
1
or R
2
represents an alkynyl group, a carbon-carbon triple bond is preferably located at the position &bgr; to the C═X moiety. When either of R
1
or R
2
represents an alkynyl group, the compound of formula (1) preferably has the triple bond in conjugation with the iminium group.
Aryl groups which may be represented by one or more of R
1
, R
2
, and R
5
to R
24
may contain 1 ring or 2 or more fused rings which may include cycloalkyl, aryl or heterocyclic rings. Examples of aryl groups which may be represented by R
1
, R
2
, and R
5
to R
24
include phenyl, tolyl, fluorophenyl, chlorophenyl, bromophenyl, trifluoromethylphenyl, anisyl, naphthyl and ferrocenyl groups.
Perhalogenated hydrocarbyl groups which may be represented by one or more of R
1
, R
2
, and R
5
to R
24
independently include perhalogenated alkyl and aryl groups, and any combination thereof, such as aralkyl and alkaryl groups. Examples of perhalogenated alkyl groups which may be represented by R
1
, R
2
, and R
5
to R
24
include —CF
3
and —C
2
F
5
.
Heterocyclic groups which may be represented by one or more of R
1
, R
2
, and R
5
to R
24
independently include aromatic, saturated and partially unsaturated ring systems and may comprise 1 ring or 2 or more fused rings which may include cycloalkyl, aryl or heterocyclic rings. The heterocyclic group will contain at least one heterocyclic ring, the largest of which will commonly co

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