Synlett 2023; 34(18): 2215-2219
cluster
Modern Boron Chemistry: 60 Years of the Matteson Reaction
Hemiboronic Acid-Catalyzed Reduction of α,β-Unsaturated Ketones with Reagent-Controlled Chemoselectivity
Jason P. G. Rygus
,
Daniel B. Boateng
,
Dennis G. Hall∗
We thank the Natural Sciences and Engineering Research Council of Canada (grant RGPIN-2017-05086 for D.G.H.; CGS-D scholarship for J.P.G.R.) and the Province of Alberta for financial support.
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
Supporting Information
Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1720074.
Supporting Information
Publication History
Received: 17 April 2023
© 2023. Thieme. All rights reserved
Georg Thieme Verlag KG
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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%), Et3 SiH (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 . 1 H 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). 13 C 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 C18 H16 NaO3 : 303.0992; found: 303.0993.
