An Efficient Route to Branched Allylsilanes through Copper-Catalyzed Allene Hydrosilylation Using Readily Available Silanes

Abstract

A CuCl-catalyzed hydrosilylation of allenes with PhSiH₃ has been developed. It is the first example of using readily available cheap silane reagents to generate branched allylsilanes in copper-catalyzed allene hydrosilylation. This base-metal catalyst offered an atom-economical and efficient route to branched allylsilanes with excellent regioselectivity.

Key words

copper - hydrosilylation - allenes - branched allylsilanes - regioselectivity

Publication History

Received: 25 March 2022

Accepted after revision: 20 April 2022

Accepted Manuscript online:
20 April 2022

Article published online:
06 May 2022

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• 11 Typical Experimental Procedure for the Synthesis of 3a In a nitrogen-filled Schlenk tube, CuCl (10 mol%), L1 (10 mol%), and THF (2 mL) were added and stirred for 5 min, then 1a (0.3 mmol), phenylsilane (0.33 mmol), and NaEt₃BH (20 mol%) were added under N₂. The reaction mixture was stirred at 60 °C for 24 h. Upon completion, the solvent was removed by vacuum, and the crude residue was purified by silica gel column chromatography to afford the corresponding products 3a as colorless liquid (84%, 66 mg). Characterization Data of 3a ¹H NMR (500 MHz, CDCl₃): δ = 7.63–7.51 (m, 2 H), 7.42–7.30 (m, 3 H), 5.73 (ddd, J = 17.2, 10.2, 9.1 Hz, 1 H), 4.93 (dd, J = 10.3, 0.8 Hz, 1 H), 4.89 (dd, J = 17.3, 1.3 Hz, 1 H), 4.29–4.19 (m, 2 H), 2.06–1.96 (m, 1 H), 1.59–1.48 (m, 2 H), 1.46–1.33 (m, 2 H), 1.29–1.22 (m, 10 H), 0.87 (t, J = 7.0 Hz, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 139.6, 135.7, 131.4, 129.7, 127.9, 113.2, 31.9, 30.13, 30.08, 29.5, 29.4, 29.3, 29.1, 22.7, 14.1. HRMS (ESI): m/z calcd for C₁₇H₂₈NaSi⁺ [M + Na]⁺: 283.1852; found: 283.1851.