Organopromoted Direct Synthesis of 1,1-Diphenyl-3-arylindanes via Formal [3+2] Cycloadditions of Triphenylcarbenium Tetrafluoroborate with Styrenes

Abstract

A formal [3+2] cycloaddition of triphenylcarbenium tetrafluoroborate with structurally different styrene derivatives has been developed. A combination of benzophenone and Et₃N is key for promoting a formal [3+2] cycloaddition of triphenylcarbenium tetrafluoroborate with styrenes affording 1,1-diphenyl-3-arylindanes in moderate to good yields. The reaction mechanism of this transformation is also discussed.

Key words

styrenes - triphenylcarbenium tetrafluoroborate - indanes - formal [3+2] cycloaddition - organocatalyst

• References and Notes

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• 16 General Procedure for the Synthesis of 1,1,3-Triphenylindane (6a) A round-bottom flask equipped with a magnetic stirrer bar was charged with styrene (1.0 mmol), benzophene (0.3 mmol), Et₃N (1.0 mmol), and toluene (2.5 mL). Triphenylcarbenium tetrafluoroborate (1.5 mmol) was then added, and the resulting mixture was allowed to react at 80 °C for 48 h. After the end of the reaction, the mixture was filtered through a plug of Celite^® and eluted with hexane–EtOAc (8:2). The filtrate was concentrated in vacuo and purified by column chromatography on silica gel. The final product 6a was obtained in 77% yield as a white solid, mp 111.5–112.5 °C. Analytical TLC on silica gel: R _ƒ = 0.40 (hexanes–EtOAc = 9.9:0.1). IR (KBr): ν_max = 3080, 3061, and 3025 (aromatic), 2966, 2928, and 2862 (CH of aliphatic), 1596, and 1491 (aromatic), 1470, 1454, and 1444 (CH of aliphatic) cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 7.35–7.16 (m, 17 H), 7.1 (d, J = 6.8 Hz, 1 H), 6.92 (d, J = 6.8 Hz, 1 H), 4.2 (dd, J = 6.4, 11.1 Hz, 1 H), 3.2 (dd. J = 6.4, 12.6 Hz, 1 H), 2.90 (dd, 11.1, 12.6 Hz, 1 H). ¹³C NMR (75 MHz, CDCl₃): δ = 149.41 (C), 148.05 (C), 146.66, (C), 145.83 (C), 143.88 (C), 128.61 (3 CH), 128.54 (3 CH), 128.52 (2 CH), 128.03 (2 CH), 127.99 (2 CH), 127.19 (CH), 126.72 (CH), 126.62 (CH), 126.28 (CH), 126.08 (CH), 126.04 (CH), 125.03 (CH), 60.84 (C), 54.13 (CH₂), 49.01 (CH). HRMS (ESI-TOF): m/z [M + Na]⁺ calcd for C₂₇H₂₂Na: 369.1619; found: 369.1531.