Imminoamines and preparation thereof
AssigneeBoard of Trustees of Michigan State University
InventorAaron L. Odom
Life of this patent
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Abstract
A process is described for producing one or more substituted iminoamines, in particular β-unsaturated β-iminoamines, in a single reaction comprising reacting one or more primary amines, alkynes, and isonitriles in the presence of a transition metal catalytic complex, preferably a titanium metal catalytic complex such as (N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti(NMe2)2(dpma)), under reaction conditions effective for 3-component coupling of the primary amines, alkynes, and isonitriles to produce one or more of the substituted iminoamines.
Claims62
1- A process for producing a substituted iminoamine which comprises:
- reacting a primary amine, an alkyne, and an isonitrile in the presence of a catalytic complex comprising a transition metal and a ligand under reaction conditions effective for coupling the nitrogen of the primary amine to a first carbon of the triple carbon-carbon bond of the alkyne and coupling the nitrile carbon of the isonitrile to the second carbon of the triple carbon-carbon bond of the alkyne to produce the substituted iminoamine.
2- The process of claim 1 wherein the primary amine is selected from the group consisting of aryl amines, cyclic amines, alkylamines, substituted aryl amines, substituted cyclic amines, substituted alkylamines, and combinations thereof.
3- The process of claim 1 wherein the alkyne is selected from the group of consisting of terminal alkynes, internal alkynes, substituted terminal alkynes, substituted internal alkynes, and combinations thereof.
4- The process of claim 1 wherein the isonitrile is selected from the group consisting of alkyl isonitriles, aryl nitrites, substituted alkyl isonitriles, substituted aryl nitrites, and combinations thereof.
5- The process of claim 1 wherein the transition metal is selected from the group consisting of titanium, zirconium, hafnium, and unnilquadium.
6- The process of claim 1 wherein the ligand is selected from the group consisting of cyclopentadienyl, thiolate, pyrrolyl, amido, guandininate, and derivatives thereof.
7- The process of claim 1 wherein the ligand is a chelating pyrrolyl-based ligand selected from the group consisting of N,N-di(pyrrolyl-α-methyl)-N-methylamine (dpma), 5,5-dimethyl-dipyrrolylmethane) (dmpm), 5,5-dipropyl-dipyrrolylmethane (dppm), 5-methyl-5-(5-ethylene-bicyclo[2.1.1]hept-2-ene-dipyrrolylmethane (mnpm), and derivatives thereof.
8- The process of claim 1 wherein the catalytic complex is selected from the group consisting of bis(dimethylamido)(N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti (NMe2) 2 (dpma)), (bis(dimethylamido)(5,5-dipropyl-dipyrrolylmethane)titanium (Ti (NMe2)2 (dppm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dmpm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2)2 (mnpm)), and derivatives thereof.
9- The process of claim 1 wherein the catalytic complex is anchored to a surface of a substrate.
10- The process of claim 9 wherein the substrate is glass or a polymer.
11- The process of claim 9 wherein the substrate is selected from the group consisting of norbornene, polystyrene, and derivatives thereof.
12- The process of any one of claims 9, 10, or 11 wherein the catalytic complex is selected from the group consisting of bis(dimethylamido) (N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti (NMe2)2(dpma)), (bis(dimethylamido)(5,5-dipropyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dppm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dmpm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (mnpm)), and derivatives thereof.
13- A process for producing a substituted α,β-unsaturated β-iminoamine which comprises:
- reacting a primary amine, an alkyne, and an isonitrile in the presence of a catalytic complex comprising a transition metal and a ligand under reaction conditions effective for coupling the nitrogen of the primary amine to a first carbon of the triple carbon-carbon bond of the alkyne and coupling nitrile carbon of the isonitrile to the second carbon of the triple carbon-carbon bond of the alkyne to produce the substituted α,β-unsaturated β-iminoamine.
14- The process of claim 13 wherein the primary amine is selected from the group consisting of aryl amines, cyclic amines, alkylamines, substituted aryl amines, substituted cyclic amines, substituted alkylamines, and combinations thereof.
15- The process of claim 13 wherein the alkyne is selected from the group of consisting of terminal alkynes, internal alkynes, substituted terminal alkynes, substituted internal alkynes, and combinations thereof.
16- The process of claim 13 wherein the isonitrile is selected from the group consisting of alkyl isonitriles, aryl nitrites, substituted alkyl isonitriles, substituted aryl nitrites, and combinations thereof.
17- The process of claim 13 wherein the transition metal is selected from the group consisting of titanium, zirconium, hafnium, and unnilquadium.
18- The process of claim 13 wherein the ligand is selected from the group consisting of cyclopentadienyl, thiolate, pyrrolyl, amido, guandininate, and derivatives thereof.
19- The process of claim 13 wherein the ligand is a chelating pyrrolyl-based ligand selected from the group consisting of N,N-di(pyrrolyl-α-methyl)-N-methylamine (dpma), 5,5-dimethyl-dipyrrolylmethane) (dmpm), 5,5-dipropyl-dipyrrolylmethane (dppm), 5-methyl-5-(5-ethylene-bicyclo[2.1.1]hept-2-ene-dipyrrolylmethane (mnpm), and derivatives thereof.
20- The process of claim 13 wherein the catalytic complex is selected from the group consisting of bis(dimethylamido)(N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti (NMe2)2 (dpma)), (bis(dimethylamido)(5,5-dipropyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dppm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2)2 (dmpm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (mnpm)), and derivatives thereof.
21- The process of claim 13 wherein the catalytic complex is anchored to a surface of a substrate.
22- The process of claim 21 wherein the substrate is glass or a polymer.
23- The process of claim 21 wherein the substrate is selected from the group consisting of norbornene, polystyrene, and derivatives thereof.
24- The process of any one of claims 21, 22, or 23 wherein the catalytic complex is selected from the group consisting of bis(dimethylamido)(N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti (NMe2)2(dpma)), (bis(dimethylamido)(5,5-dipropyl-dipyrrolylmethane)titanium (Ti (NMe2)2 (dppm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dmpm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (mnpm)), and derivatives thereof.
25- A process for producing a library of substituted iminoamines which comprises:
- reacting one or more primary amines, one or more alkynes, and one or more isonitriles in the presence of a catalytic complex comprising a transition metal and a ligand under reaction conditions effective for coupling the nitrogen of the primary amine to a first carbon of the triple carbon-carbon bond of the alkyne and coupling nitrile carbon of the isonitrile to the second carbon of the triple carbon-carbon bond of the alkyne to produce the library of substituted iminoamines.
26- The process of claim 25 wherein the primary amines are selected from the group consisting of aryl amines, cyclic amines, alkylamines, substituted aryl amines, substituted cyclic amines, substituted alkylamines, and combinations thereof.
27- The process of claim 25 wherein the alkynes are selected from the group of consisting of terminal alkynes, internal alkynes, substituted terminal alkynes, substituted internal alkynes, and combinations thereof.
28- The process of claim 25 wherein the substituted isonitriles are selected from the group consisting of alkyl isonitriles, aryl nitrites, substituted alkyl isonitriles, substituted aryl nitrites, and combinations thereof.
29- The process of claim 25 wherein the transition metal is selected from the group consisting of titanium, zirconium, hafnium, and unnilquadium.
30- The process of claim 25 wherein the ligand is selected from the group consisting of cyclopentadienyl, thiolate, pyrrolyl, amido, guandininate, and derivatives thereof.
31- The process of claim 25 wherein the ligand is a chelating pyrrolyl-based ligand selected from the group consisting of of N,N-di(pyrrolyl-α-methyl)-N-methylamine (dpma), 5,5-dimethyl-dipyrrolylmethane) (dmpm), 5,5-dipropyl-dipyrrolylmethane (dppm), 5-methyl-5-(5-ethylene-bicyclo[2.1.1]hept-2-ene-dipyrrolylmethane (mnpm), and derivatives thereof.
31- The process of claim 25 wherein the catalytic complex is selected from the group consisting of bis(dimethylamido)(N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti (NMe2) 2 (dpma)), (bis(dimethylamido)(5,5-dipropyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dppm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dmpm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (mnpm)), and derivatives thereof.
33- The process of claim 25 wherein the catalytic complex is anchored to a surface of a substrate.
34- The process of claim 33 wherein the substrate is glass or a polymer.
35- The process of claim 33 wherein the substrate is selected from the group consisting of norbornene, polystyrene, and derivatives thereof.
36- The process of any one of claims 33, 34, or 35 wherein the catalytic complex is selected from the group consisting of bis(dimethylamido)(N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti (NMe2)2(dpma)), (bis(dimethylamido)(5,5-dipropyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dppm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dmpm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2)2 (mnpm)), and derivatives thereof.
37- A process for producing a substituted α,β-unsaturated β-iminoamine which comprises:
- reacting a primary amine, an alkyne, and an isonitrile in the presence of a catalytic complex comprising a transition metal and a ligand selected from the group consisting of cyclopentadienyl, thiolate, pyrrolyl, amido, guandininate, and derivatives thereof under reaction conditions effective for coupling the nitrogen of the primary amine to a first carbon of the triple carbon-carbon bond of the alkyne and coupling nitrile carbon of the isonitrile to the second carbon of the triple carbon-carbon bond of the alkyne to produce the substituted α,β-unsaturated β-iminoamine.
38- The process of claim 37 wherein the primary amine is selected from the group consisting of aryl amines, cyclic amines, alkylamines, substituted aryl amines, substituted cyclic amines, substituted alkylamines, and combinations thereof.
39- The process of claim 37 wherein the alkyne is selected from the group of consisting of terminal alkynes, internal alkynes, substituted terminal alkynes, substituted internal alkynes, and combinations thereof.
40- The process of claim 37 wherein the isonitrile is selected from the group consisting of alkyl isonitriles, aryl nitrites, substituted alkyl isonitriles, substituted aryl nitrites, and combinations thereof.
41- The process of claim 37 wherein the transition metal is selected from the group consisting of titanium, zirconium, hafnium, and unnilquadium.
42- The process of claim 37 wherein the ligand is a chelating pyrrolyl-based ligand selected from the group consisting of N,N-di(pyrrolyl-α-methyl)-N-methylamine (dpma), 5,5-dimethyl-dipyrrolylmethane) (dmpm), 5,5-dipropyl-dipyrrolylmethane (dppm), 5-methyl-5-(5-ethylene-bicyclo[2.1.1]hept-2-ene-dipyrrolylmethane (mnpm), and derivatives thereof.
43- The process of claim 37 wherein the catalytic complex is selected from the group consisting of bis(dimethylamido)(N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti (NMe2) 2 (dpma)), (bis(dimethylamido)(5,5-dipropyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dppm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dmpm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (mnpm)), and derivatives thereof.
44- The process of claim 37 wherein the catalytic complex is anchored to a surface of a substrate.
45- The process of claim 44 wherein the substrate is glass or a polymer.
46- The process of claim 44 wherein the substrate is selected from the group consisting of norbornene, polystyrene, and derivatives thereof.
47- The process of any one of claims 44, 45, or 46 wherein the catalytic complex is selected from the group consisting of bis(dimethylamido)(N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti(NMe2)2(dpma)), (bis(dimethylamido)(5,5-dipropyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dppm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dmpm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2)2 (mnpm)), and derivatives thereof.
48- A process for producing a substituted α,β-unsaturated β-iminoamine which comprises:
- reacting a primary amine, an alkyne, and an isonitrile in the presence of a catalytic complex comprising a transition metal and a ligand anchored to the surface of a substrate under reaction conditions effective for coupling the nitrogen of the primary amine to a first carbon of the triple carbon-carbon bond of the alkyne and coupling nitrile carbon of the isonitrile to the second carbon of the triple carbon-carbon bond of the alkyne to produce the substituted α,β-unsaturated β-iminoamine.
49- The process of claim 48 wherein the primary amine is selected from the group consisting of aryl amines, cyclic amines, alkylamines, substituted aryl amines, substituted cyclic amines, substituted alkylamines, and combinations thereof.
50- The process of claim 48 wherein the alkyne is selected from the group of consisting of terminal alkynes, internal alkynes, substituted terminal alkynes, substituted internal alkynes, and combinations thereof.
51- The process of claim 48 wherein the isonitrile is selected from the group consisting of alkyl isonitriles, aryl nitrites, substituted alkyl isonitriles, substituted aryl nitrites, and combinations thereof.
52- The process of claim 48 wherein the transition metal is selected from the group consisting of titanium, zirconium, hafnium, and unnilquadium.
53- The process of claim 48 wherein the ligand is selected from the group consisting of cyclopentadienyl, thiolate, pyrrolyl, amido, guandininate, and derivatives thereof.
54- The process of claim 48 wherein the ligand is a chelating pyrrolyl-based ligand selected from the group consisting of N,N-di(pyrrolyl-α-methyl)-N-methylamine (dpma), 5,5-dimethyl-dipyrrolylmethane) (dmpm), 5,5-dipropyl-dipyrrolylmethane (dppm), 5-methyl-5-(5-ethylene-bicyclo[2.1.1]hept-2-ene-dipyrrolylmethane (mnpm), and derivatives thereof.
55- The process of claim 48 wherein the catalytic complex is selected from the group consisting of bis(dimethylamido)(N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti (NMe2) 2 (dpma)), (bis(dimethylamido)(5,5-dipropyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dppm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dmpm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2)2 (mnpm)), and derivatives thereof.
56- The process of claim 48 wherein the substrate is glass or a polymer.
57- The process of claim 56 wherein the substrate is selected from the group consisting of norbornene, polystyrene, and derivatives thereof.
58- The process of claim 56 or 57 wherein the catalytic complex is selected from the group consisting of bis(dimethylamido)(N,N-di(pyrrolyl-α-methyl)-N-methylamine)titanium (Ti (NMe2) 2 (dpma)), (bis(dimethylamido)(5,5-dipropyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (dppm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2)2 (dmpm)), bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti (NMe2) 2 (mnpm)), and derivatives thereof.
59- A compound which is (bis(dimethylamido) (5,5-dipropyl-dipyrrolylmethane)titanium (Ti(NMe2)2 (dppm)).
60- A compound which is bis(dimethylamido)(5,5-dimethyl-dipyrrolylmethane)titanium (Ti(NMe2)2 (mnpm)).
61- A compound selected from the group consisting of
- 24
- wherein Ph is phenyl, Me is methyl, Cy is cyclohexyl, But is t-butyl, and Bun is n-butyl.
62- A substituted iminoamine which has the formula
- 25
- wherein each R is independently selected from the group consisting of hydrogen, methyl, alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl linear or branched, combinations thereof, and substituted derivatives thereof.