Chemo-, Regio-, and Stereoselective Access to (E)-Boryl-Substituted Allyl Fluorides via Electrophilic Fluorodesilylation

Abstract

Herein, we report a transition-metal-free chemo-, regio-, and stereoselective electrophilic fluorodesilylation of α-silyl-substituted allylboronate esters. α-Silyl-substituted allylboronate esters can be chemoselectively coupled with Selectfluor, resulting in a variety of (E)-boryl-substituted allyl fluorides in good yields with γ- and (E)-selectivities. The utilities of the obtained (E)-boryl-substituted allyl fluorides are highlighted by further modifications to afford allyl or alkyl fluoride derivatives.

Key words

allyl fluorides - chemoselectivity - fluorodesilylation - regio­selectivity - stereoselectivity

Publication History

Received: 20 April 2023

Accepted after revision: 09 May 2023

Accepted Manuscript online:
09 May 2023

Article published online:
14 June 2023

• References and Notes

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• 12 Typical Procedure for the Preparation of Product 3a: In a nitrogen-filled glovebox, Selectfluor 2a (71 mg, 0.20 mmol) and anhydrous acetonitrile (1.0 mL) were added to an oven-dried 4.0 mL dram vial equipped with a Teflon-coated magnetic stirrer bar. The vial was removed from the glovebox and cooled to 0 °C. (E)-Trimethyl(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)but-2-en-1-yl) (1a, 0.24 mmol, 1.2 equiv) in anhydrous acetonitrile solution (1.0 mL) was added dropwise to the solution, under an argon atmosphere. The reaction mixture was stirred at 0 °C for 12 h and then passed through a short pad of celite and washed with CH₂Cl₂ (50 mL). The filtrate was concentrated under reduced pressure. The ¹H NMR yield was determined by using anisole as an internal standard (96%). The crude mixture was purified by column chromatography on silica gel (n-hexane/Et₂O = 80:1 to 20:1) to give the corresponding product 3a as a light yellow oil (33 mg, 83%, E/Z = 13:1). ¹H NMR (500 MHz, CDCl₃): δ = 6.64–6.57 (ddd, J = 18.2, 16.4, 4.6 Hz, 1 H), 5.70–5.65 (m, 1 H), 5.16–5.02 (m, 1 H), 1.43–1.37 (dd, J = 23.7, 6.5 Hz, 3 H), 1.27 (s, 12 H). ¹³C NMR (126 MHz, CDCl₃): δ = 151.2 (d, J = 19.7 Hz), 90.4 (d, J = 167.1 Hz), 83.6, 24.9 (24.91), 24.9 (24.90), 20.9 (d, J = 23.5 Hz). ¹¹B NMR (161 MHz, CDCl₃): δ = 29.8. ¹⁹F NMR (471 MHz, CDCl₃): δ = –167.8 (minor isomer), –172.7 (major isomer).