Facile Protocols towards C2-Arylated Benzoxazoles using Fe(III)-Catalyzed C(sp2-H) Functionalization and Metal-Free Domino 
Approach

Nagaraju Vodnala; Raghuram Gujjarappa; Arup K. Kabi; Mohan Kumar; Uwe Beifuss; Chandi C. Malakar

doi:10.1055/s-0037-1609718

Synlett, Table of Contents

Synlett 2018; 29(11): 1469-1478
DOI: 10.1055/s-0037-1609718

letter

Facile Protocols towards C2-Arylated Benzoxazoles using Fe(III)-Catalyzed C(sp ²-H) Functionalization and Metal-Free Domino Approach

Nagaraju Vodnala

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal 795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

,

Raghuram Gujjarappa

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal 795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

,

Arup K. Kabi

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal 795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

,

Mohan Kumar

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal 795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

,

Uwe Beifuss

^bInstitut für Chemie, Universität Hohenheim, Garbenstr. 30, 70599 Stuttgart, Germany

,

Chandi C. Malakar *

^aDepartment of Chemistry, National Institute of Technology Manipur, Langol, Imphal 795004, Manipur, India Email: cmalakar@nitmanipur.ac.in

› Author Affiliations

Abstract

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Abstract

Considering their growing attention in the field of medicinal chemistry and drug-discovery research, the facile and convenient approaches towards the preparation of 2-aryl benzoxazole derivatives have been described. The transformation is accomplished by using Fe(III)-catalyzed C–H activation of benzoxazoles with boronic acids to obtain a wide range of C2-arylated benzoxazoles in high yields. The developed method excludes the formation of self-coupling compounds as side products. On the other hand, the synthesis of the products is also achieved via a metal-free domino protocol by the reaction between 1-nitroso-2-naphthol and acetophenones using catalytic amounts of CBr₄ in the presence of Cs₂CO₃ as base. The devised tandem method avoids the use of pre-activated α-haloketones as substrates. Due to their immense impact in marketed drugs and molecules under clinical trial, the described method can be a powerful tool for their synthesis which restricts the use of precious metals as catalyst.

Key words

benzoxazoles - Fe(III)-catalysis - C-arylation - C–H Activation - domino reaction

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References

References and Notes

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21 General Experimental Procedure for the Synthesis of Products 3a–v: Method A: A-10 mL pressure tube was charged with a mixture of 1a–f (1.0 mmol), 2a–o (1.0 mmol), FeCl₃ (0.05 mmol, 8.1 mg), 1,10-phenanthroline (0.1 mmol, 18 mg), DCIB (1.3 mmol, 165 mg), Cs₂CO₃ (1.5 mmol 487 mg), and DMF (2 mL). The pressure tube was then sealed and heated at 100 °C for 16 h. After completion of the reaction, the mixture was diluted with hot EtOAc (50 mL) and H₂O (100 mL) and extracted with EtOAc (3 × 50 mL). The combined organic layer was washed with brine (2 × 50 mL) and dried over anhyd Na₂SO₄. The solvent was removed under reduced pressure and the remaining residue was purified by flash chromatography over silica gel using hexane–EtOAc (10:1) as an eluent to obtain the desired products 3a–v. Method B: In an oven-dried 100-mL round-bottomed flask 4a–b (1.0 mmol), 5a–k (1.0 mmol), CBr₄(0.5 mmol, 165 mg), Cs₂CO₃ (2.1 mmol, 682 mg) and 10 mL MeCN (10 mL) were added successively and the reaction mixture was heated for 6 h at 80 °C under nitrogen atmosphere. The reaction mixture was allowed to cool to r.t. and then the solvent was removed under vacuum. The crude product was purified by using column chromatography over silica gel using hexane–EtOAc (10:1) as an eluent to get the products 3a–f, 3h, 3i, 3k, 3m, 3w, 3x as yellow crystalline solids.
22 Characterization Data for 2-Phenylnaptho[1,2-d]oxazole (3a): yield: 85%, 208 mg (Method A) and 69%, 169 mg (Method B). ¹H NMR (400 MHz, CDCl₃): δ = 7.45–7.49 (m, 5 H, 8-H, 9-H, 10-H, 11-H, 12-H), 7.69 [dd, ³ J (1-H, 2-H) = 7.0 Hz, ³ J (2-H, 3-H) = 8.0 Hz, ³ J (3-H, 4-H) = 8.1 Hz, ³ J (2-H, 3-H), 2 H, 2-H, 3-H], 7.89 [d, ³ J (3-H, 4-H) = 7.0 Hz, 1 H, 4-H], 8.23–8.29 [m, ³ J (5-H, 6-H)= 8.9 Hz, 2 H, 5-H, 6-H], 8.52 [d, ³ J (1-H, 2-H) = 8.0 Hz, 1 H, 1-H]. ¹³C NMR (100 MHz, CDCl₃): δ = 109.8 (C-6), 115.5 (C-14), 121.2 (C-1), 123.4 (C-15), 124.3 (C-2), 124.9 (C-3), 125.9 (C-4), 126.2 (C-8, C-12), 127.5 (C-10), 127.8 (C-9, C-11), 130.0 (C-5), 130.1 (C-19), 136.5(C-16), 147.0 (C-17), 161.2 (C-18). HRMS (EI): m/z [M + H]⁺ calcd for C₁₇H₁₂NO: 246.0918; found: 246.0914.

Supplementary Material

Supporting Information

Facile Protocols towards C2-Arylated Benzoxazoles using Fe(III)-Catalyzed C(sp 2-H) Functionalization and Metal-Free Domino Approach

Facile Protocols towards C2-Arylated Benzoxazoles using Fe(III)-Catalyzed C(sp ²-H) Functionalization and Metal-Free Domino Approach