Copper(I)-Catalyzed Diastereoselective Borylative Exo-Cyclization of Alkenyl Aryl Ketones

Abstract

Copper(I)-catalyzed diastereoselective borylative exo-cyclization of alkenyl ketones with bis(pinacolato)diboron is reported. The reaction of alkenyl aryl ketones under a CuCl/Xantphos catalyst system provides four- or five-membered-ring syn-2-(borylmethyl)cycloalkanol derivatives in good yields with high syn selectivities. The utility of this method is demonstrated by further transformations of the cyclic products.

Key words

boron - cyclization - stereoselective synthesis - copper - catalysis

• References and Notes


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• 17 Typical Procedure for the Borylative Cyclization/Esterification of Aryl Alkenyl Ketones: CuCl (0.025 mmol) and (pin)B–B(pin) (0.60 mmol), Xantphos (0.025 mmol), t-BuOK (0.60 mmol) were placed in an oven-dried vial in a glove box. After the vial was removed from the glove box, DME (1.0 mL) was added to the vial and stirred for 30 min. Then, 1a (0.50 mmol) was added to the mixture at 30 °C. After the reaction was complete, the reaction mixture was cooled to 0 °C. After that, DMAP [0.05 mmol in THF (1 mL)] and i-Pr₂NEt (0.52 mmol) were added to the mixture, and 4-(trifluoromethyl)benzoyl chloride (0.53 mmol) was added dropwise. After the reaction was complete, the reaction mixture was passed through a short florisil column eluting with Et₂O. The crude material was purified by silica gel column chromatography to give syn-4a (129.7 mg, 0.282 mmol, 56% yield) as a white solid. ¹H NMR (392 MHz, CDCl₃): δ = 1.25 (s, 6 H), 1.26 (s, 6 H), 1.36 (dd, J = 10.0, 15.9 Hz, 1 H), 1.46 (dd, J = 6.3, 15.7 Hz, 1 H), 1.68–1.79 (m, 1 H), 2.06–2.16 (m, 1 H), 2.62–2.72 (m, 1 H), 2.80–2.91 (m, 1 H), 2.97–3.07 (m, 1 H), 7.21–7.28 (m, 1 H), 7.30–7.36 (m, 2 H), 7.47–7.51 (m, 2 H), 7.68 (d, J = 7.8 Hz, 2 H), 8.20 (d, J = 7.8 Hz, 2 H). ¹³C NMR (99 MHz, CDCl₃): δ = 12.5 (br, BCH₂), 23.0 (CH₂), 24.80 (Me), 24.86 (Me), 30.2 (CH₂), 44.0 (CH), 83.2 (C), 85.4 (C), 125.0 (q, J _C–F = 273.8 Hz, C), 125.1 (CH), 125.2–152.4 (m, CH), 127.2 (CH), 128.3 (CH), 130.0 (CH), 134.22 (q, J _C–F = 32.7 Hz, C), 134.28 (C), 143.1 (C), 163.8 (C). HRMS (ESI): m/z [M + Na]⁺ calcd for C₂₅H₂₈O₄BF₃Na: 482.19613; found: 482.19653.
• 18 Several derivatization methods were examined to improve the isolated yield, but these were not successful.
• 19 The cuprate-carbonyl π complex may be formed in this step; see: Bertz SH, Hardin RA, Heavey TJ, Ogle CA. Angew. Chem. Int. Ed. 2013; 52: 10250