Structure of 34598-50-0
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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Bashar, Noorul ; Kundu, Bidyut Kumar ; Pozdeev, Anton S ; Jiang, De-en ; Sun, Yujie ;
Abstract: Aryl radicals serve as essential intermediates in contemporary organic synthesis, facilitating diverse carbon−carbon and carbon-heteroatom bond-forming reactions under mild conditions. Aryl halides, widely available and frequently employed as precursors for photocatalytic aryl radical generation, typically require photocatalysts with strong reducing capabilities to overcome their high reduction potentials. Herein, we report an innovative approach for the photocatalytic generation of aryl radicals using an organic photocatalyst 5,5′-bis((4-methoxyphenyl)ethynyl)-2,2′-bibenzo[d]thiazole (dBAP) that leverages the proton-coupled electron transfer (PCET) mechanism. This strategy allows the selective generation of aryl radicals at the ortho and para positions of aryl halides bearing PCET handles, despite dBAP’s intrinsic reducing power being insufficient for direct electron transfer to the aryl halides, in contrast to the prevalent approaches. Mechanistic investigations highlight the role of PCET in lowering the activation barrier for aryl radical formation, enabling efficient C−H, C−C, and C−B bond-forming reactions with high regioselectivity and functional group tolerance. This work underscores the potential of PCET-driven photocatalysis using organic photocatalysts as a sustainable and versatile platform for expanding the synthetic utility of aryl radicals under ambient conditions.
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Purchased from AmBeed: 42348-86-7 ; 34598-50-0 ; 46258-62-2 ; 3988-03-2 ; 2001-29-8 ; 214701-49-2 ; 16184-89-7 ; 2142-63-4 ; 99-90-1 ; 10342-83-3 ; 2142-69-0 ; 99-91-2
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CAS No. : | 34598-50-0 |
Formula : | C9H9BrO |
M.W : | 213.07 |
SMILES Code : | OC1CCC2=C1C=CC(Br)=C2 |
MDL No. : | MFCD06808667 |
InChI Key : | DRXIUUZVRAOHBS-UHFFFAOYSA-N |
Pubchem ID : | 13486299 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302 |
Precautionary Statements: | P280-P305+P351+P338 |
Num. heavy atoms | 11 |
Num. arom. heavy atoms | 6 |
Fraction Csp3 | 0.33 |
Num. rotatable bonds | 0 |
Num. H-bond acceptors | 1.0 |
Num. H-bond donors | 1.0 |
Molar Refractivity | 47.93 |
TPSA ? Topological Polar Surface Area: Calculated from |
20.23 Ų |
Log Po/w (iLOGP)? iLOGP: in-house physics-based method implemented from |
2.31 |
Log Po/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by |
2.15 |
Log Po/w (WLOGP)? WLOGP: Atomistic method implemented from |
2.1 |
Log Po/w (MLOGP)? MLOGP: Topological method implemented from |
2.51 |
Log Po/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by |
2.85 |
Consensus Log Po/w? Consensus Log Po/w: Average of all five predictions |
2.38 |
Log S (ESOL):? ESOL: Topological method implemented from |
-2.92 |
Solubility | 0.257 mg/ml ; 0.0012 mol/l |
Class? Solubility class: Log S scale |
Soluble |
Log S (Ali)? Ali: Topological method implemented from |
-2.21 |
Solubility | 1.32 mg/ml ; 0.00621 mol/l |
Class? Solubility class: Log S scale |
Soluble |
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by |
-3.28 |
Solubility | 0.112 mg/ml ; 0.000524 mol/l |
Class? Solubility class: Log S scale |
Soluble |
GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg |
High |
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg |
Yes |
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) |
No |
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) |
Yes |
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) |
No |
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) |
No |
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) |
No |
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) |
No |
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from |
-6.07 cm/s |
Lipinski? Lipinski (Pfizer) filter: implemented from |
0.0 |
Ghose? Ghose filter: implemented from |
None |
Veber? Veber (GSK) filter: implemented from |
0.0 |
Egan? Egan (Pharmacia) filter: implemented from |
0.0 |
Muegge? Muegge (Bayer) filter: implemented from |
1.0 |
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat |
0.55 |
PAINS? Pan Assay Interference Structures: implemented from |
0.0 alert |
Brenk? Structural Alert: implemented from |
0.0 alert: heavy_metal |
Leadlikeness? Leadlikeness: implemented from |
No; 1 violation:MW<1.0 |
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) |
2.19 |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine; In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; diethyl ether; toluene; | 5-Bromoindene A 1 L three-neck round bottom flask equipped with a condenser, magnetic stir bar, nitrogen inlet, and a thermometer was charged with 5-bromo-1-indanol (56.5 g, 0.265 mol), toluene (300 mL), pyridine (250 mL, 3.1 mol), and p-toluenesulfonyl chloride (55.3 g, 0.29 mol). The mixture was stirred and heated to reflux while dehydration progress was followed by GC. After 7 hours at reflux the dark colored reaction mixture was cooled, quenched by pouring over ice-water (700 mL) containing HCI (12M, 200 mL) and extracted several times with diethyl ether (3 x 250 mL). The combined diethyl ether extracts were washed repeatedly with water, 5% sodium bicarbonate (aqueous), and water then dried over anhydrous magnesium sulfate. Evaporation of diethyl ether followed by vacuum distillation (80 C / 0.5 mm Hg) gave 5-bromoindene (24.0 g, 99+% purity by GC) as a colorless oil. 1H-NMR (CD2Cl2, 500 MHz) delta 7.59 (br s, 1H); 7.38 (dd, JAB=1.5, 8 Hz, 1H), 7.26 (d, JAB=8 Hz, 1H); 6.84 (m, 1H); 6.56 (m, 1H); 3.39 (s, 2H). |
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