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. 2024 May 20;63(20):9164-9174.
doi: 10.1021/acs.inorgchem.4c00499. Epub 2024 May 8.

Synthesis and Regioselective Functionalization of Tetrafluorobenzo-[α]-Fused BOPYPY Dyes

Sebastian O Oloo  1 , Guanyu Zhang  1 , Petia Bobadova-Parvanova  2 , Seleen Al Horani  2 , Masa Al Horani  2 , Frank R Fronczek  1 , Kevin M Smith  1 , Maria da Graça H Vicente  1
Affiliations

Synthesis and Regioselective Functionalization of Tetrafluorobenzo-[α]-Fused BOPYPY Dyes

Sebastian O Oloo et al. Inorg Chem. .

Abstract

The synthesis of a new bis-BF2 tetrafluorobenzo-[α]-fused BOPYPY dye from 4,5,6,7-tetrafluoroisoindole and 2-hydrazinopyrazine is reported. The regioselectivity of nucleophilic substitution reactions at the periphery of the tetrafluorinated BOPYPY and its α-bromo derivative were investigated using N-, O-, S-, and C-based nucleophiles. Among the aromatic fluorine atoms, the F2 atom is consistently regioselectively substituted, except when the α-position contains a thiophenol group; in this case, F4 is substituted instead due to stabilizing π-π-stacking between the two aromatic groups. The α-bromo BOPYPY derivative also reacts under Stille cross-coupling reaction conditions to produce the corresponding α-substituted product. The spectroscopic properties of these new fluorinated BOPYPYs were investigated and compared with nonfluorinated analogs.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Core structures of BODIPY and bisBF2 derivatives BOPHY, BOPPY, and BOPYPY.
Scheme 1
Scheme 1. Synthesis of BOPYPY 1 and Its Brominated Derivative 2
Figure 2
Figure 2
X-ray crystal structures of BOPYPY 1 (left) and its brominated derivative 2 (right) with 50% ellipsoids.
Scheme 2
Scheme 2. Regioselective SNAr Reactions of BOPYPY 1 Using 4-Methoxythiophenol
Scheme 3
Scheme 3. Regioselective SNAr Reactions of BOPYPY 2 with S, O, N, and C Nucleophiles
Figure 3
Figure 3
X-ray crystal structures of BOPYPYs 4a, 4c, 4d, and 4e with 50% ellipsoids.
Scheme 4
Scheme 4. Regioselective SNAr Reactions on Select BOPYPYs 4
Figure 4
Figure 4
X-ray crystal structures of disubstituted BOPYPYs 5a, 5b, 5c, and 7 with 50% ellipsoids.
Scheme 5
Scheme 5. Regioselective SNAr Reactions with Different Regioselectivity
Scheme 6
Scheme 6. Regioselective Stille Cross-Coupling Reaction of BOPYPY 2
Figure 5
Figure 5
Chemical structures of previously reported BOPYPY 8(16) and BOPPY 9.
Figure 6
Figure 6
Frontier MO diagram for BOPYPY 1. Energies in eV. Calculated at the TD-DFT M06-2X/6-31+G(d,p) level in dichloromethane.
See this image and copyright information in PMC

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