Direct oxidative amination of hydrocarbons

1. A process for converting a hydrocarbon comprising at least one C—H bond to a nitrogen-functionalized product, comprising

contacting the hydrocarbon and

(i) an oxidizing electrophile comprising

(a) a main group element selected from the group consisting of arsenic, selenium, indium, tin, antimony, tellurium, thallium, lead, and bismuth in oxidized form and

(b) at least one nitrogen-containing ligand of the formula —NH n Y 2-n , wherein Y is deactivated aryl, —F, —COR, —C(O)OR, —C(O)NRR′, —NO 2 , —NO, —CH 2 SO 2 , —SO 2 R, —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or P(O)RR′, wherein R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic,

wherein the deactivated aryl comprises at least one electron withdrawing substituent selected from —NO 2 , fluoro-C 1-8 alkyl, —F, —OOCR″, —COOH, —OH 2 + , —CONH 2 , —COOR″, —NR″ 3 + , —CN, —SO 3 H, —SO 3 R″, —SO 3 W, and a combination thereof, wherein R″ is hydrogen or an aliphatic, heteroaliphatic, aromatic, or heteroaromatic moiety, each of which is optionally substituted, W is a cation comprising a metal selected from boron, bismuth, antimony, arsenic, lanthanum, cerium, scandium, yttrium, titanium, zirconium, hafnium, silver, zinc, cadmium, aluminum, gallium, indium, germanium, tin, phosphorus, an alkali metal, and an alkaline earth metal, and

n is 0 or 1, or

(ii) an oxidant and a reduced form of an oxidizing electrophile comprising (a) a main group element selected from the group consisting of arsenic, selenium, indium, tin, antimony, tellurium, thallium, lead, and bismuth and (b) at least one nitrogen-containing ligand of the formula —NH n Y 2-n , wherein Y is deactivated aryl, —F, —COR, —C(O)OR, —C(O)NRR′, —NO 2 , —NO, —CH 2 SO 2 , —SO 2 R, —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or —P(O)RR′, wherein R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic,

wherein the deactivated aryl comprises at least one electron withdrawing substituent selected from —NO 2 , fluoro-C 1-8 alkyl, —F, —OOCR″, —COOH, —OH 2 + , —CONH 2 , —COOR″, —NR″ 3 + , —CN, —SO 3 H, —SO 3 R″, —SO 3 W, and a combination thereof, wherein R″ is hydrogen or an aliphatic, heteroaliphatic, aromatic, or heteroaromatic moiety, each of which is optionally substituted, and W is a cation comprising a metal selected from boron, bismuth, antimony, arsenic, lanthanum, cerium, scandium, yttrium, titanium, zirconium, hafnium, silver, zinc, cadmium, aluminum, gallium, indium, germanium, tin, phosphorus, an alkali metal, and an alkaline earth metal, and

n is 0 or 1,

in a solvent to provide the nitrogen-functionalized product and an electrophile reduction product; and

optionally separating the nitrogen-functionalized product and the electrophile reduction product,

wherein

the hydrocarbon is selected from alkane, alkene, alkyne, cycloalkane, cycloalkene, heterocycloalkane, heterocycloalkene, arene, and heteroarene, each of which is optionally substituted,

the hydrogen in the at least one C—H bond has been replaced with —NH n Y 2-n from the at least one nitrogen-containing ligand, and

the process does not contain an added halide ion.

2. The process of claim 1 , comprising separating the nitrogen-functionalized product and the electrophile reduction product.

3. The process of claim 1 , further comprising contacting the nitrogen-functionalized product with a compound of the formula H—Nu, which is a neutral or charged species, to form an NH 2 -containing compound, wherein Nu is a nucleophilic group that enables the formation of the NH 2 -containing compound.

4. The process of claim 3 , wherein Nu comprises oxide, hydroxide, alkoxide, aryloxide, carboxylate, thiolate, bisulfide, optionally protected amide, or optionally protected azanide.

5. The process of claim 3 , wherein Nu is —O, —OR 1 , —CO 2 R 1 , —S, —SR 1 , —NR 1 , —NHR 1 , or —NR 1 R 2 , in which R 1 and R 2 are the same or different and each is hydrogen, aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

6. The process of claim 3 , wherein the NH 2 -containing compound comprises a monoamine, a diamine, or both a monoamine, and a diamine.

7. The process of claim 1 , further comprising contacting the electrophile reduction product and an oxidizing regeneration reagent to regenerate the oxidizing electrophile.

8. The process of claim 1 , wherein the hydrocarbon is selected from alkane, cycloalkane, and arene, each of which is optionally substituted.

9. The process of claim 1 , wherein the oxidizing electrophile comprises the element thallium, lead, antimony, selenium, tellurium, or bismuth.

10. The process of claim 1 , wherein Y is deactivated aryl, —F, —NO 2 , —NO, —CH 2 SO 2 , —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or —P(O)RR′, wherein R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic, wherein the deactivated aryl comprises at least one electron withdrawing substituent selected from —NO 2 , fluoro-C 1-8 alkyl, —F, —OOCR″, —COOH, —OH 2 + , —CONH 2 , —COOR″, —NR″ 3 + , —CN, —SO 3 H, —SO 3 R″, —SO 3 W, and a combination thereof, wherein R″ is hydrogen or an aliphatic, heteroaliphatic, aromatic, or heteroaromatic moiety, each of which is optionally substituted, and W is a cation comprising a metal selected from boron, bismuth, antimony, arsenic, lanthanum, cerium, scandium, yttrium, titanium, zirconium, hafnium, silver, zinc, cadmium, aluminum, gallium, indium, germanium, tin, phosphorus, an alkali metal, and an alkaline earth metal.

11. The process of claim 1 , wherein Y is —COR, —C(O)OR, —C(O)NRR′, or —SO 2 R, wherein R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

12. The process of claim 1 , wherein the oxidizing electrophile is of the formula M m (NH n Y 2-n ) p L q , wherein

M is a cation of the main group element,

Y is deactivated aryl, —F, —COR, —C(O)OR, —C(O)NRR′, —NO 2 , —NO, —CH 2 SO 2 , —SO 2 R, —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or —P(O)RR′, wherein R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic,

wherein the deactivated aryl comprises at least one electron withdrawing substituent selected from —NO 2 , fluoro-C 1-8 alkyl, —F, —OOCR″, —COOH, —OH 2 + , —CONH 2 , —COOR″, —NR″ 3 + , —CN, —SO 3 H, —SO 3 R″, —SO 3 W, and a combination thereof, wherein R″ is hydrogen or an aliphatic, heteroaliphatic, aromatic, or heteroaromatic moiety, each of which is optionally substituted, and W is a cation comprising a metal selected from boron, bismuth, antimony, arsenic, lanthanum, cerium, scandium, yttrium, titanium, zirconium, hafnium, silver, zinc, cadmium, aluminum, gallium, indium, germanium, tin, phosphorus, an alkali metal, and an alkaline earth metal,

L is a ligand,

m is the formal oxidation state of M,

n is 0 or 1,

p is 1 to m, and

q is 0 to 5.

13. The process of claim 12 , wherein m is 1-8.

14. The process of claim 1 , wherein the solvent is a non-oxidizable liquid selected from a fluorinated hydrocarbon, a sulfone, a deactivated arene, a deactivated aliphatic, a deactivated heteroarene, a deactivated heteroaliphatic, a compound of the formula HNY 2 or H 2 NY, and any combination thereof, wherein Y is aryl, —F, —COR, —C(O)OR, —C(O)NRR′, —NO 2 , —NO, —CH 2 SO 2 , —SO 2 R, —SO 2 F, —SO 2 OH, —SO 2 NH 2 , or —P(O)RR′, and R and R′ are the same or different and each is aliphatic, heteroaliphatic, aromatic, or heteroaromatic.