Chemodiversity in the Palladium-Catalyzed Cyclizations of ­Allenynecarboxylates

Abstract

Pd-catalyzed cyclizations of 1,n-allenynecarboxylates have been found to exhibit three different cyclization modes: cycloreduction, arylative cyclization, and [2+2] cycloaddition depending on the reaction conditions.

Key words

palladium - allenyne - cycloreduction - arylative cyclization - cycloaddition

References

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8

A typical procedure for the Pd-catalyzed intramolecular [2+2] cycloaddition of allenyne 1: In a 5 mL test tube allenyne 1 (101.2 mg, 0.314 mmol), PdCl_{2 (}PPh₃)₂ (11.2 mg, 0.0156 mmol), and anhyd toluene (1.5 mL) were added. The resulting mixture was stirred for 10 min at r.t. and for 12 h at 110 °C. The reaction mixture was concentrated and separated by silica gel chromatography (eluent: ethyl acetate-hexane (1:4) to give the cycloaddition product 4 (77.1 mg, 76%) as a colorless oil. IR (neat): 2981, 2883, 1731, 1681, 1622, 1486, 1369, 1298, 1239, 1198, 1101, 1056, 908, 758 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 5.55 (t, J = 4.0 Hz, 1 H), 4.18-4.23 (m, 6 H), 3.16 (t, J = 2.8 Hz, 2 H), 3.07 (t, J = 2.8 Hz, 2 H), 2.81 (d, J = 4.0 Hz, 2 H), 1.31 (t, J = 7.6 Hz, 3 H), 1.23 (t, J = 6.8 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 170.30, 163.38, 152.86, 136.76, 128.50, 114.25, 61.76, 60.12, 35.51, 31.10, 29.65, 14.55, 14.08. HRMS: m/z calcd for C₁₇H₂₂O₆ (M⁺): 322.1416; found: 322.1427. All products were fully characterized by ¹H, ¹³C NMR, and IR spectroscopy and HRMS.