Compositions and methods of promoting organic photocatalysis
The invention provides novel compounds and methods that are useful in promoting reactions that proceed through an oxidative quenching pathway. In certain embodiments, the reactions comprise atom transfer radical polymerization.
1. A method of promoting reaction of at least one reagent, the method comprising:
irradiating with electromagnetic radiation the at least one reagent in the presence of an organic compound, or a salt or solvate thereof, selected from the group consisting of:
wherein:
each occurrence of R is independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 1 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O) (C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl),
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R; and
each occurrence of R 4 , R 5 R 6 , and R 7 is independently selected from the group consisting of phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, triphenylamino, phenanthrenyl, and pyrenyl, each of which is independently substituted with at least one R,
wherein:
if the compound is
then
each occurrence of R is independently selected from the group consisting of C 2 -C 6 alkyl, C 1 -C 6 haloalkyl, substituted phenyl, —O(C 2 -C 6 alkyl), —NO 2 , —C(═O)OH, —C(═O)O(C 2 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O) (C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl);
if the compound is
then
each occurrence of R is independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 2 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O) (C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl);
if the compound is
then
each occurrence of R 1 is independently selected from the group consisting of 1-naphthyl and 2-naphthyl, each of which is independently substituted with at least one R.
2. The method of claim 1 , wherein the reaction comprises at least one selected from the group consisting of atom transfer radical addition/polymerization, dehalogenation, cycloaddition, cyclization, dimerization, coupling, reduction, ring-opening, alkylation, arylation, oxygenation, energy transfer, electron transfer, radical substitution, and radical addition.
3. The method of claim 1 , wherein the reaction comprises atom transfer radical addition/polymerization.
4. The method of claim 1 , wherein the at least one reagent comprises a (meth)acrylate and an organic halide.
5. The method of claim 4 , wherein the organic halide comprises an α-halo ester.
6. The method of claim 1 , wherein the reaction is essentially free of a metal or metalloid.
7. The method of claim 1 , wherein the radiation comprises visible light.
8. The method of claim 7 , wherein the radiation comprises sunlight or a natural light source.
9. The method of claim 7 , wherein the radiation comprises radiation provided by a LED.
10. The method of claim 1 , wherein R 1 is 1-naphthyl or R 1 is phenyl substituted by at least one substituent selected from the group consisting of CF 3 and C(═O)OH.
11. The method of claim 10 , wherein the compound is selected from the group consisting of:
12. The method of claim 1 , wherein the organic compound has the structure of
wherein
R 1 is independently selected from the group consisting of 1-naphthyl and 2-naphthyl, each of which is independently substituted with at least one R; and
R 2 and R 3 are independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R.
13. The method of claim 12 , wherein if the compound is
then R 1 is 1-naphthyl.
14. The method of claim 13 , wherein the organic compound has the structure:
15. The method of claim 1 , wherein the organic compound has the structure:
wherein
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R; and
each occurrence of R 4 , R 5 R 6 , and R 7 is independently selected from the group consisting of phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, triphenylamino, phenanthrenyl, and pyrenyl, each of which is independently substituted with at least one R, and
each occurrence of R is independently selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 2 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O) (C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl).
16. The method of claim 15 , wherein the organic compound is
17. The method of claim 1 , wherein the reaction comprises a carbon-carbon bond formation coupling reaction, carbon-nitrogen bond formation coupling reaction, carbon-oxygen bond formation coupling reaction, carbon-sulfur bond formation coupling reaction, or a carbon-phosphorus bond formation coupling reaction.
18. The method of claim 17 , wherein the reaction comprises an aryl carbon-aryl carbon bond formation coupling reaction, aryl carbon-alkyl carbon bond formation coupling reaction, aryl carbon-vinyl carbon bond formation coupling reaction, aryl carbon-nitrogen bond formation coupling reaction, aryl carbon-oxygen bond formation coupling reaction, aryl carbon-sulfur bond formation coupling reaction, or an aryl carbon-phosphorus bond formation coupling reaction.
19. The method of claim 17 , wherein the carbon-carbon bond formation coupling reaction comprises an alkyl carbon-alkyl carbon bond formation coupling reaction.
20. The method of claim 2 , wherein the radical substitution or radical addition comprises reaction with a vinyl group or an aromatic group.
21. A method of promoting reaction of at least one reagent, the method comprising:
irradiating with electromagnetic radiation the at least one reagent in the presence of an organic compound, or a salt or solvate thereof, selected from the group consisting of:
wherein:
each occurrence of R is independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 1 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O) (C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl),
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R; and
each occurrence of R 4 , R 5 R 6 , and R 7 is independently selected from the group consisting of phenyl, 4-phenyl-phenyl, 1-naphthyl, 2-naphthyl, triphenylamino, phenanthrenyl, and pyrenyl, each of which is independently substituted with at least one R.
22. The method of claim 21 , wherein the organic compound has the structure
wherein
each occurrence of R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R;
each occurrence of R 2 and R 3 is independently selected from the group consisting of phenyl and 4-phenyl-phenyl, each of which is independently substituted with at least one R.
23. The method of claim 21 , having the structure of:
wherein R 1 is independently selected from the group consisting of phenyl, 1-naphthyl, and 2-naphthyl, each of which is independently substituted with at least one R.
24. The method of claim 21 , wherein the reaction comprises at least one selected from the group consisting of atom transfer radical addition/polymerization, dehalogenation, cycloaddition, cyclization, dimerization, coupling, reduction, ring-opening, alkylation, arylation, oxygenation, energy transfer, electron transfer, radical substitution, and radical addition.
25. The method of claim 21 , wherein the reaction comprises atom transfer radical addition/polymerization.
26. The method of claim 21 , wherein the at least one reagent comprises a (meth)acrylate and an organic halide.
27. The method of claim 21 , wherein the reaction comprises a carbon-carbon bond formation coupling reaction, carbon-nitrogen bond formation coupling reaction, carbon-oxygen bond formation coupling reaction, carbon-sulfur bond formation coupling reaction or a carbon-phosphorus bond formation coupling reaction.
28. The method of claim 27 , wherein the reaction comprises an aryl carbon-aryl carbon bond formation coupling reaction, aryl carbon-alkyl carbon bond formation coupling reaction, aryl carbon-vinyl carbon bond formation coupling reaction, aryl carbon-nitrogen bond formation coupling reaction, aryl carbon-oxygen bond formation coupling reaction, aryl carbon-sulfur bond formation coupling reaction, or an aryl carbon-phosphorus bond formation coupling reaction.
29. The method of claim 27 , wherein the carbon-carbon bond formation coupling reaction comprises an alkyl carbon-alkyl carbon bond formation coupling reaction.
30. The method of claim 24 , wherein the radical substitution or radical addition comprises reaction with a vinyl group or an aromatic group.
31. A method of promoting reaction of at least one reagent, the method comprising:
irradiating with electromagnetic radiation the at least one reagent in the presence of an organic compound, or a salt or solvate thereof, selected from the group consisting of:
wherein R is independently selected from the group consisting of H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, optionally substituted phenyl, —OH, —O(C 1 -C 6 alkyl), —NO 2 , —CN, —C(═O)OH, —C(═O)O(C 1 -C 6 alkyl), —C(═O)O-phenyl, —C(═O)(C 1 -C 6 alkyl), —C(═O)-phenyl, —S(O) 2 NH 2 , —S(O) 2 NH(C 1 -C 6 alkyl), —S(O) 2 N(C 1 -C 6 alkyl)(C 1 -C 6 alkyl), —S(C 1 -C 6 alkyl), —S(O) (C 1 -C 6 alkyl), —S(O) 2 (C 1 -C 6 alkyl), —S(phenyl), —S(O)(phenyl), and —S(O) 2 (phenyl).
32. The method of claim 31 , wherein the reaction comprises at least one selected from the group consisting of atom transfer radical addition/polymerization, dehalogenation, cycloaddition, cyclization, dimerization, coupling, reduction, ring-opening, alkylation, arylation, oxygenation, energy transfer, electron transfer, radical substitution, and radical addition.
33. The method of claim 31 , wherein the reaction comprises atom transfer radical addition/polymerization.
34. The method of claim 31 , wherein the at least one reagent comprises a (meth)acrylate and an organic halide.
35. The method of claim 31 , the reaction comprises a carbon-carbon bond formation coupling reaction, carbon-nitrogen bond formation coupling reaction, carbon-oxygen bond formation coupling reaction, carbon-sulfur bond formation coupling reaction, or a carbon-phosphorus bond formation coupling reaction.
36. The method of claim 35 , wherein the reaction comprises an aryl carbon-aryl carbon bond formation coupling reaction, aryl carbon-alkyl carbon bond formation coupling reaction, aryl carbon-vinyl carbon bond formation coupling reaction, aryl carbon-nitrogen bond formation coupling reaction, aryl carbon-oxygen bond formation coupling reaction, aryl carbon-sulfur bond formation coupling reaction, or an aryl carbon-phosphorus bond formation coupling reaction.
37. The method of claim 35 , wherein the carbon-carbon bond formation coupling reaction comprises an alkyl carbon-alkyl carbon bond formation coupling reaction.
38. The method of claim 32 , wherein the radical substitution or radical addition comprises reaction with a vinyl group or an aromatic group.