Hemiboronic Acid-Catalyzed Reduction of α,β-Unsaturated Ketones with Reagent-Controlled Chemoselectivity

Dedicated to Professor Donald Matteson in recognition of his ­seminal contributions to organoboron chemistry.

Abstract

The use of an air-stable cationic hemiboronic acid catalyst for the chemoselective reduction of enones is described. By changing the identity and stoichiometry of the silane reducing agent, either the conjugate reduction products or the fully reduced products can be obtained in high selectivity. In contrast to analogous reactions catalyzed by air- and moisture-sensitive borane catalysts, the hemiboronic acid catalyzed protocol can be performed under ambient conditions. Profiling studies revealed that global reduction proceeds via a rapid initial 1,4-addition, followed by ketone deoxygenation with a rate that is highly silane-dependent.

Key words

boronic acid catalysis - hemiboronic acids - reduction - deoxygenation - silanes

Publikationsverlauf

Eingereicht: 17. April 2023

Angenommen nach Revision: 16. Mai 2023

Artikel online veröffentlicht:
23. Juni 2023

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• 41a 4-(3-Phenylpropanoyl)phenyl acrylate (3h); Typical Procedure Under air, a vial was charged with enone 2h (111 mg, 0.400 mmol), catalyst 1 (4.0 mg, 0.020 mmol, 5 mol%), Et₃SiH (80 μL, 0.50 mmol, 1.25 equiv), and HFIP (1.6 mL). The mixture was stirred at rt for 24 h, then concentrated by rotary evaporation. Purification by column chromatography [silica gel, hexane–EtOAc (gradient 30:1 to 20:1)] gave a viscous oil; yield: 92 mg (83%). FTIR (microscope): 3063 (w), 3028 (w), 2927 (w), 1743 (m), 1686 (m), 1599 (m), 1405 (m), 1204 (s), 1146 (s), 980 (m), 799 (w), 750 (w) cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 8.03 (d, J = 8.8 Hz, 2 H), 7.33–7.30 (m, 2 H), 7.27–7.21 (m, 5 H), 6.65 (dd, J = 17.4, 1.3 Hz, 1 H). 6.34 (dd, J = 17.4, 10.5 Hz, 1 H), 6.07 (dd, J = 10.4, 1.2 Hz, 1 H). 3.31 (t, J = 7.8 Hz, 2 H), 3.09 (t, J = 7.7 Hz, 2 H). ¹³C NMR (126 MHz, CDCl₃): δ = 198.1, 164.1, 154.4, 141.3, 134.6, 133.4, 129.8, 128.7, 128.6, 127.7, 126.3, 121.9, 40.6, 30.2. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₈H₁₆NaO₃: 303.0992; found: 303.0993.