The Formation of C(sp3)-C(sp3) by Visible-Light Photocatalysis

doi:10.7536/PC180820

We summarize the latest results of C(sp ³)-C(sp ³) coupling by visible-light photoredox catalysis in recent years and focus on the catalytic systems, reaction mechanisms and practical applications in synthesizing bioactivity molecules or drug molecules. Indeed, introducing transition metals or chiral catalysts in the visible light-catalyzed reaction system and the constructing of a novel synergistic catalysis system can make the precise formation of the C(sp ³)-C(sp ³) bond under mild conditions become a reality, which will have important implications for the design and development of chiral drugs. Finally, the future development of visible-light photoredox catalysis is prospected.

Key words: visible-light photocatalysis, C—C bond;, synergistic catalysis, asymmetric catalysis

Scheme. 1 Representative photocatalysts

Table 1 The photophysical properties of photocatalysts[5,6,17]

Photocatalyst	$λ max a$	τ^b	$E 1 c$	$E 2 d$
Ru(bpy)₃(PF₆)₂	452	1100	-0.81	+0.77
Mes-Acr⁺Cl $O 4 -$	430	-	-	+2.06
Ir[dF(CF₃)ppy]₂(dtbpy)(PF₆)	380	2300	-0.89	+1.21
Ir(ppy)₂(dtbpy)(PF₆)	-	557	-0.96	+0.66
Ir(ppy)₃	375	1900	-1.73	+0.31

Table 1 The photophysical properties of photocatalysts[5,6,17]

Photocatalyst	$λ max a$	τ^b	$E 1 c$	$E 2 d$
Ru(bpy)₃(PF₆)₂	452	1100	-0.81	+0.77
Mes-Acr⁺Cl $O 4 -$	430	-	-	+2.06
Ir[dF(CF₃)ppy]₂(dtbpy)(PF₆)	380	2300	-0.89	+1.21
Ir(ppy)₂(dtbpy)(PF₆)	-	557	-0.96	+0.66
Ir(ppy)₃	375	1900	-1.73	+0.31

Fig. 1 The relationship between photocatalysts, substrates and oxidant and reductant

Scheme. 2 Shuttle and quenching of single electron[2]

Scheme. 3 Decarboxylative medicated by visible-light for Michael addition reaction[32]

Scheme. 4 Oxalates as activating groups for alcohols in visible light photoredox catalysis[33]

Scheme. 5 The formation of C(sp3)-C(sp3) bonds using carboxylic acids and alkyl halides[34]

Scheme. 6 Proposed mechanism of decarboxylation coupling to generate C(sp3)-C(sp3) bonds[34]

Scheme. 7 The synthesis of the antiplatelet drug tirofiban

Scheme. 8 Proposed mechanism for the decarboxylative peptide macrocyclization[37]

Scheme. 9 Decarboxylative allylation by photoredox catalysis and application in oligosaccharide[38]

Scheme. 10 A coupling reaction between benzylic ethers and Schiff bases[39]

Scheme. 11 Radical-radical cross-couplings to synthesize γ-aminoketones[40]

Scheme. 12 The effect of DABCO on the regioselectivity in coupling reaction

Scheme. 13 The mechanism of spin-center shift

Scheme. 14 Reaction system and substrate scopes[44]

Scheme. 15 Enantioselective synthesis of stereoselective translocator protein(18 kDa) ligand PK-14067[45]

Scheme. 16 Enantioselective conjugate additions of α-amino radicals via cooperative photoredox and Lewis acid catalysis[46]

Scheme. 17 Putative mechanism for the visible-light-activated catalytic asymmetric process[47]

Scheme. 18 The importance of nitrogen atom in pyridine

Scheme. 19 Allylation modification of complexed molecules in gram scale[53]

Scheme. 20 Visible-light-induced allylation and intermolecular Michael addition reaction of aldehydes, ketones and imines[54]

Scheme. 21 The chiral iridium complex provides asymmetric induction for the enantioselective alkylation of 2-acyl imidazoles[55]

Scheme. 22 Putative mechanism for the visible-light activated catalytic asymmetric process[56]

Scheme. 23 Ruthenium/rhodium synergetic catalysis to synthesize chiral 1,2-aminoalcohols[57]

Scheme. 24 Enantioselective additions to α,β-unsaturated ketones mediated by visible-light photoredox catalysis[58]

Scheme. 25 Radical translocation and stereocontrolled alkene addition mediated by visible-light photoredox catalysis[59]

Scheme. 26 Visible light photoredox catalysed intermolecular radical addition of α-halo amides to olefins[60]

Scheme. 27 Visible-light photoredox catalyzed Giese reaction[61]

Scheme. 28 Proposed photoredox catalytic cycle for the synthesis of 1,2-diamines[65]

Scheme. 29 Direct access to vicinal diamines and amino alcohols via α-amino radicals and ketyl radicals[65]

Scheme. 30 The synthesis of 1,4-diketones by means of a visible light-induced C—S bond activation process[66]

Scheme. 32 Two-step construction of heterocycles[66]

Scheme. 33 Putative mechanism for the direct synthesis of polysubstituted aldehydes[69]

Scheme. 34 Direct synthesis of polysubstituted aldehydes via visible-light catalysis[69]

Scheme. 35 Photochemical domain and thermal domain[70, 71]

Scheme. 36 Visible-light excitation of iminium ions enables the enantioselective catalytic β-alkylation of enals[70, 71]

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The Formation of C(sp³)-C(sp³) by Visible-Light Photocatalysis

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The Formation of C(sp³)-C(sp³) by Visible-Light Photocatalysis