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Synlett 2023; 34(12): 1409-1414
DOI: 10.1055/a-1954-3236
DOI: 10.1055/a-1954-3236
cluster
Special Issue Honoring Masahiro Murakami’s Contributions to Science
Alkenylboronic Ester Activation to Nucleophilic Addition and Electrophilic Trapping with Carbonyl Groups
We are grateful for funding from the Ministerio de Economía y Competitividad y por el Fondo Europeo de Desarrollo Regional FEDER (project PID2019-109674GB-I00). S.G. is grateful for an FI grant.
Dedicated to Professor Masahiro Murakami for his inspiring research career
Abstract
Carbolithiation of (1-phenylvinyl)boronic acid pinacol ester with tert-butyllithium was used to generate α-phenylboryl carbanions that reacted in a straightforward manner with carbonyl groups through a boron–Wittig sequence. When unhindered α,β-unsaturated carbonyl compounds were used, 1,4-addition of the α-phenylboryl carbanions was observed over the boron–Wittig sequence.
Key words
alkenylboronates - alkylideneboranes - boron–Wittig reaction - boron ate suppression - boryl carbanionsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1954-3236.
- Supporting Information
Publication History
Received: 02 September 2022
Accepted after revision: 30 September 2022
Accepted Manuscript online:
30 September 2022
Article published online:
02 November 2022
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- 30 1,2-Dicarbofunctionalization through Boron–Wittig Olefination with Aldehydes or Ketones; General Method A flame-dried 100 mL round-bottomed flask equipped with a magnetic stirrer bar was charged with 4,4,5,5-tetramethyl-2-(1-phenylvinyl)-1,3,2-dioxaborolane (1) (69.5 mg, 0.3 mmol, 1.0 equiv) in dried THF (2 mL), then sealed with a rubber septum and placed under a N2 atmosphere at –78 °C. A 1.7 M solution of t-BuLi in hexane (0.19 mL, 0.33 mmol, 1.1 equiv) was added dropwise and the mixture was stirred for 30 min at –78 °C and then at rt for 16 h. The appropriate aldehyde or ketone (0.45 mmol, 1.5 equiv) was added dropwise and the mixture was stirred for 4 h at rt. Finally, the reaction was quenched with MeOH (5 mL) and the mixture was extracted with Et2O (×3). The combined organic layers were dried (MgSO4) filtered through Celite, and concentrated under reduced pressure. The NMR yield was calculated by comparison with an internal standard (naphthalene). The crude product was purified by flash column chromatography. [(1E/1Z)-1-(2,2-Dimethylpropyl)-3-methylbut-1-en-1-yl]benzene (2) Purified by flash column chromatography [silica gel, pentane–EtOAc, (100:0)] to give a colorless liquid; yield: 45.3 mg (70%, E/Z = 1:1). 1H NMR (400 MHz, CDCl3): δ = 7.34–7.25 (m, 6 H), 7.25–7.17 (m, 4 H), 5.41 (d, J = 10.0 Hz, 1 H), 5.24 (d, J = 10.1 Hz, 1 H), 2.68 (m, 1 H), 2.50 (s, 2 H), 2.43 (m, 1 H), 2.31 (s, 2 H), 1.03 (d, J = 6.5 Hz, 6 H), 0.95 (d, J = 6.6 Hz, 6 H), 0.79 (s, 9 H), 0.76 (s, 9 H). 13C NMR (100 MHz, CDCl3): δ = 145.7, 142.4, 139.5, 138.1, 135.7, 135.5, 128.1, 127.4, 127.2, 126.3, 125.5, 125.5, 52.6, 41.9, 31.8, 31.4, 29.9, 29.5, 27.7, 27.2, 23.0, 22.5. HRMS (ESI): m/z [M + H]+ calcd for C16H25: 217.1956; found: 217.1953.