Photoredox-mediated cobalt catalysis for non-asymmetric and asymmetric synthesis
Source abstract
Abstract
Visible-light-induced transition-metal catalysis is becoming essential in organic synthesis, offering sustainable and mild routes to complex molecules. Among these, photoredox-mediated cobalt catalysis has emerged as a particularly promising approach. Cobalt’s capacity to direct stereochemistry stems from its diverse redox behavior, geometric flexibility, and the ability to transition between octahedral and tetrahedral configurations. Additionally, its redox-adaptive ligand fields and spin-state plasticity play crucial roles. Recent advances have produced efficient catalytic systems capable of novel photochemical transformations, particularly in synthesizing enantiomerically enriched compounds. However, challenges remain, particularly concerning the regulation of high-energy intermediates and the mitigation of competing thermal processes. Achieving stringent stereoselectivity remains a critical hurdle, requiring integration of coordination chemistry and photophysics. This review traces the development of photoredox-mediated cobalt catalysis, emphasizing recent progress in asymmetric catalysis. By analyzing mechanisms and applications, we aim to highlight both the potential and current limitations, thereby guiding future research and innovation in photoredox-mediated cobalt catalysis field. Chi et al. present a comprehensive overview of organic transformations facilitated by photoredox-mediated cobalt catalysis, with a particular emphasis on asymmetric catalysis. The authors assess the current capabilities and limitations of this strategy, providing valuable insights that pave the way for future research and innovation in the field.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Catalytic C–H Functionalization Methods · Radical Photochemical Reactions · Sulfur-Based Synthesis Techniques
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (100+)
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1. Transition metal-catalyzed organic reactions under visible light: recent developments and future perspectives10.1021/acscatal.0c01979 ↗
2. C–H bond functionalization by dual catalysis: merging of high-valent cobalt and photoredox catalysis10.1039/D1CC04872D ↗
3. Recent advances in photochemical asymmetric three-component reactions10.1002/tcr.202300275 ↗
4. Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis10.1021/cr300503r ↗
5. Visible light-induced transition metal catalysis10.1021/acs.chemrev.1c00403 ↗
6. Direct carboxylation with carbon dioxide via dooperative photoredox and pransition-metal dual catalysis10.1002/adsc.202001280 ↗
7. Photocatalytic enantioselective hydrosulfonylation of α,β-unsaturated carbonyls with sulfonyl chlorides10.1002/anie.202312780 ↗
8. Nickel/photoredox-catalyzed three-component silylacylation of acrylates via chlorine photoelimination10.1039/D4SC02164A ↗
9. Azobenzene-integrated NHC ligands: a versatile platform for visible-light-switchable metal catalysis10.1021/jacs.4c01138 ↗
10. Photochemical asymmetric palladium-catalyzed allylation reaction: expeditious entry to chiral 1,2-amino alcohols and 1,2-diamines10.1021/acscatal.4c04209 ↗
11. Nickel-catalyzed regioselective hydrothiolation of allenes enabled by visible-light photoredox catalysis10.1021/acs.orglett.4c01027 ↗
12. Photo- and cobalt-catalyzed synthesis of heterocycles via cycloisomerization of unactivated olefins10.1002/anie.202319515 ↗
13. Photoredox/nickel dual catalysis for C(sp2)–C(sp3) cross-electrophile coupling reaction of mesylates of phenols and primary alcohols10.1021/acscatal.4c03975 ↗
14. Room-temperature C–H arylation: merger of pd-catalyzed C–H functionalization and visible-light photocatalysis10.1021/ja208068w ↗
15. Single-electron transmetalation in organoboron cross-coupling by photoredox/nickel dual catalysis10.1126/science.1253647 ↗
16. Enantioselective decarboxylative arylation of α-amino acids via the merger of photoredox and nickel catalysis10.1021/jacs.5b13211 ↗
17. The photophysics of photoredox catalysis: a roadmap for catalyst design10.1039/C6CS00526H ↗
18. Organic photoredox catalysis10.1021/acs.chemrev.6b00057 ↗
19. Photoredox-catalyzed C–H functionalization reactions10.1021/acs.chemrev.1c00311 ↗
20. Transition metal and photocatalyst free arylation via photoexcitable electron donor acceptor complexes:mediation and catalysis10.1002/cctc.202301526 ↗
21. The merger of photoredox and cobalt catalysis10.1016/j.trechm.2020.01.004 ↗
22. Dual photoredox and cobalt catalysis enabled transformations10.1002/ejoc.202200229 ↗
23. Cobalt/photoredox cooperative catalysis-enabled cycloaddition reactions of 1,6-diynes and related compounds10.1002/cctc.202400488 ↗
24. Biomimetic photoexcited cobaloxime catalysis in organic synthesis10.1002/anie.202405775 ↗
25. Cobaloxime-catalyzed hydrogen evolution in photoredox-facilitated small-molecule functionalization10.1002/ejoc.201901170 ↗
26. Vitamin B12 catalysed reactions10.1039/C5CS00165J ↗
27. Photochemical Sandmeyer-type halogenation of arenediazonium salts10.1002/chem.202103669 ↗
28. Advances in transition metal (Pd,Ni,Fe)-catalyzed cross-coupling reactions using alkyl-organometallics as reaction partners10.1021/cr100327p ↗
29. A photo- and cobalt-catalyzed highly selective and divergent hydrofunctionalization of 1,3-dienes with phenols10.1039/D5SC00438A ↗
30. Merging hydrogen-atom-transfer and the Truce-Smiles Rearrangement for synthesis of β-arylethylamines from unactivated allylsulfonamides
31. cis-Selective transfer semihydrogenation of alkynes by merging visible-light Catalysis with cobalt catalysis10.1002/adsc.201901562 ↗
32. Cobalt-based polymerized porphyrinic network for visible-light-driven CO2 reduction10.1021/acsami.4c04487 ↗
33. Merging dual photoredox/cobalt catalysis and boronic acid (derivatives) activation for the Minisci reaction10.1039/D2QO01441F ↗
34. An earth-abundant cobalt based photocatalyst: visible light induced direct (het)arene C–H arylation and CO2 capture10.1039/D1DT03625D ↗
35. Aerobic oxidation of diverse primary alcohols to carboxylic acids with a heterogeneous Pd–Bi–Te/C (PBT/C) catalyst10.1021/acs.oprd.7b00223 ↗
36. Reactions with a reverse gear10.1038/nchem.313 ↗
37. Computational structure–activity relationships in H2 storage: how placement of N atoms affects release temperatures in organic liquid storage materials10.1039/B705037B ↗
38. Photoredox mediated acceptorless dehydrogenative coupling of saturated N-heterocycles10.1021/acscatal.9b00123 ↗
39. Oxidative [4+2] annulation of styrenes with alkynes under external-oxidant-free conditions10.1038/s41467-018-03534-z ↗
40. Selective oxidative [4+2] imine/alkene annulation with H2 liberation induced by photo-oxidation10.1002/anie.201711359 ↗
41. Photocatalysis enabling acceptorless dehydrogenation of diaryl hydrazines at room temperature10.1021/acscatal.8b01579 ↗
42. Acceptorless dehydrogenation of small molecules through cooperative base metal catalysis10.1038/ncomms10093 ↗
43. Room temperature catalytic dehydrogenation of cyclic amines with the liberation of H2 using water as a solvent10.1039/C9GC00201D ↗
44. Photoredox/cobalt dual catalysis for visible-light-mediated alkene–alkyne coupling10.1021/acs.orglett.9b01201 ↗
45. Dual cobalt and photoredox catalysis enabled intermolecular oxidative hydrofunctionalization10.1021/acscatal.0c01209 ↗
46. Dual cobalt and photoredox catalysis enabled redox-neutral annulation of 2-propynolphenols10.1002/adsc.202100221 ↗
47. Cobalt-catalyzed enantioselective hydroetherification of alkenes and symmetric 1,3-diketones
48. Cobalt hydride-catalyzed hydroalkynylation of alkenes with alkynyl trifluoroborates10.1021/acscatal.4c02211 ↗
49. Cobalt-catalyzed HAT reaction for asymmetric hydrofunctionalization of alkenes and nucleophiles
50. Harnessing the potential of acyl triazoles in bifunctional cobalt-catalyzed radical cross-coupling reactions10.1038/s41467-024-51376-9 ↗
51. Cobalt-catalyzed photo-semipinacol rearrangement of unactivated allylic alcohols10.1002/anie.202407827 ↗
52. Intermolecular organophotocatalytic cyclopropanation of unactivated olefins10.1021/jacs.2c11680 ↗
53. A comprehensive overview of directing groups applied in metal-catalyzed C–H functionalisation chemistry10.1039/C8CS00201K ↗
54. Bidentate directing groups: an efficient tool in C–H bond functionalization chemistry for the expedient construction of C–C bonds10.1021/acs.chemrev.9b00495 ↗
55. Bidentate, monoanionic auxiliary-directed functionalization of carbon–hydrogen bonds10.1021/ar5004626 ↗
56. Recent advances in cobalt-catalysed C–H functionalizations10.1039/C9OB01994D ↗
57. Room-temperature synthesis of isoindolone spirosuccinimides: merger of visible-light photocatalysis and cobalt-catalyzed C–H activation10.1021/acs.joc.0c02120 ↗
58. Eosin Y as a redox catalyst and photosensitizer for sequential benzylic C−H amination and oxidation10.1002/chem.201804229 ↗
59. Catalytic nucleophilic ‘umpoled’ π-allyl reagents10.1039/C7CS00449D ↗
60. Nozaki−Hiyama−Kishi reactions catalytic in chromium10.1021/ja9625236 ↗
61. Reagent-controlled transition-metal-catalyzed radical reactions10.1021/cr9902648 ↗
62. Reductive radical-polar crossover: traditional electrophiles in modern radical reactions10.1039/C9SC03359A ↗
63. Catalytic photoredox allylation of aldehydes promoted by a cobalt complex10.1002/adsc.202001250 ↗
64. Mechanism switch between radical-polar crossover and radical buffering
65. A. transition metal-catalyzed cycloisomerizations of 1,n-allenynes and -allenenes10.1021/cr100376w ↗
66. Rhodium-catalyzed (5 + 2) and (5 + 1) cycloadditions using 1,4-enynes as five-carbon building blocks10.1021/acs.accounts.9b00477 ↗
67. Cobalt/organophotoredox dual catalysis-enabled cascade cyclization of 1,6-diynyl esters via formal 1,8-acyloxy migration10.1021/acscatal.1c03704 ↗
68. Hydroxyl assisted, photoredox/cobalt Co-catalyzed semi-hydrogenation and tandem cyclization of o-alkynylphenols for access to 2,3-dihydrobenzofurans10.1002/adsc.202000986 ↗
69. Photochemical deracemization of lactams with deuteration enabled by dual hydrogen atom transfer10.1021/jacs.4c14934 ↗
70. Visible light-induced HAT catalysis for the regioselective hydroacylation of N-sulfonylimine esters with aldehydes.10.1055/a-2550-1878 ↗
71. Site-selective acceptorless dehydrogenation of aliphatics enabled by organophotoredox/cobalt dual catalysis10.1021/jacs.1c05479 ↗
72. Toward a mild dehydroformylation using base-metal catalysis10.1039/C6SC04607J ↗
73. Crawley · 2012
74. Photochemical dehydrogenative strategy for aniline synthesis10.1038/s41586-020-2539-7 ↗
75. Cobaloxime catalysis: selective synthesis of alkenylphosphine oxides under visible light10.1021/jacs.9b06920 ↗
76. Cobaloxime catalysis for enamine phosphorylation with hydrogen evolution10.1021/acs.orglett.0c01709 ↗
77. Advancements in organocatalysis for radical-mediated asymmetric synthesis: A recent perspective
78. Mechanistic Investigation of Enantioconvergent Kumada Reactions of Racemic α-Bromoketones Catalyzed by a Nickel/Bis(oxazoline) Complex10.1021/jacs.9b08185 ↗
79. Stereospecific radical coupling with a non-natural photodecarboxylase10.1038/s41586-024-08004-9 ↗
80. Methods and mechanisms for cross-electrophile coupling of Csp2–halides with alkyl electrophiles10.1021/acs.accounts.5b00057 ↗
81. Highly regio- and enantioselective reductive coupling of alkynes and aldehydes via photoredox cobalt dual catalysis10.1021/jacs.1c03527 ↗
82. Photoassisted cobalt-catalyzed asymmetric reductive Grignard-type addition of aryl iodides10.1021/jacs.2c02481 ↗
83. Light-driven asymmetric coupling of aromatic aldehydes and aryl iodides using a simple amine reductant10.1039/D3GC04014C ↗
84. Photoredox cobalt-catalyzed regio-diastereo- and enantioselective propargylation of aldehydes via propargyl radicals10.1038/s41467-023-40488-3 ↗
85. A highly efficient and direct approach for synthesis of enantiopure β-amino alcohols by reductive cross-coupling of chiral N-tert-butanesulfinyl imines with aldehydes10.1021/ja054401w ↗
86. Reductive coupling between aromatic aldehydes and ketones or imines by copper catalysis10.1021/jacs.8b13309 ↗
87. Copper-catalyzed enantioselective reductive cross-coupling of aldehydes and imines10.1021/acs.orglett.9b04144 ↗
88. Cr-catalyzed asymmetric cross Aza-Pinacol couplings for β-amino alcohol synthesis10.1021/jacs.3c08493 ↗
89. Enantioselective photoredox catalysis enabled by proton-coupled electron transfer: development of an asymmetric Aza-Pinacol cyclization10.1021/ja4100595 ↗
90. Asymmetric cross-coupling of aldehydes with diverse carbonyl or iminyl compounds by photoredox-mediated cobalt catalysis10.1021/jacs.4c01443 ↗
91. Attractive natural products with strained cyclopropane and/or cyclobutane ring systems10.1007/s11426-016-0233-1 ↗
92. The “Cyclopropyl fragment” is a versatile player that frequently appears in preclinical/clinical drug molecules10.1021/acs.jmedchem.6b00472 ↗
93. Desymmetrization–addition reaction of cyclopropenes to imines via synergistic photoredox and cobalt catalysis10.1021/jacs.4c07096 ↗
94. Catalytic approaches to assemble cyclobutane motifs in natural product synthesis10.1039/C7QO00668C ↗
95. Cyclobutanes in catalysis10.1002/anie.201101053 ↗
96. The application of cyclobutane derivatives in organic synthesis10.1021/cr010010y ↗
97. Photoredox/cobalt-catalyzed chemo-regio-diastereo- and enantioselective reductive coupling of 1,1-disubstituted allenes and cyclobutenes
98. CuH-catalyzed olefin functionalization: from hydroamination to carbonyl addition10.1021/acs.accounts.0c00164 ↗
99. Mechanistic basis for regioselection and regiodivergence in nickel-catalyzed reductive couplings10.1021/acs.accounts.5b00096 ↗
100. Enantioselective metal-catalyzed reductive coupling of alkynes with carbonyl compounds and imines: convergent construction of allylic alcohols and amines10.1021/acscatal.2c02444 ↗