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Synlett 2015; 26(07): 901-906
DOI: 10.1055/s-0034-1380165
DOI: 10.1055/s-0034-1380165
letter
Copper-Catalyzed Asymmetric Conjugate Addition to α-Alkylidene Cycloalkanones
Further Information
Publication History
Received: 26 November 2014
Accepted after revision: 22 January 2015
Publication Date:
17 February 2015 (online)
Abstract
The asymmetric copper-catalyzed conjugate addition to α-alkylidene cycloalkanones, substituted at their terminal position with aromatic and aliphatic groups, is reported. While high enantioselectivity is reached using chiral phosphoramidite ligands, with R3Al reagents, moderate diastereoselectivity was observed upon hydrolysis of the aluminium enolates. A Grignard reagent also react with high diastereoselectivity.
Key words
α-alkylidene cycloalkanones - conjugate addition - copper - trialkylaluminium reagents - Grignard reagentsSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1380165.
- Supporting Information
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References and Notes
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- 12 3i: Colourless oil. Mixture of diastereomers = 4.2:1. 1H NMR (400 MHz, CD2Cl2): δ = 0.71 (d, J = 6.9 Hz, 1 H, dia minor), 0.81 (d, J = 6.8 Hz, 3 H, dia major), 0.85 (d, J = 6.8 Hz, 3 H, dia major), 0.90 (d, J = 6.7 Hz, 2 H, dia minor), 0.93 (d, J = 6.9 Hz, 3 H), 1.49–1.55 (m, 1.3 H, 2 dias), 1.61–1.81 (m, 4.3 H, 2 dias), 1.93–2.03 (m, 3.2 H, 2 dias), 2.05–2.13 (m, 1.9 H, 2 dias), 2.18–2.29 (m, 1.7 H, 2 dias). 13C NMR (100 MHz, CD2Cl2): δ = 13.4, 13.7, 18.3, 20.5, 21.1, 21.2, 21.3, 22.0, 24.7, 28.2, 30.4, 32.2, 38.8, 39.4, 39.6, 39.7, 52.6, 53.7, 220.0 (dia major), 221.7 (dia minor). IR (ATR): 2960, 2875, 1734, 1464, 1150 cm–1. HRMS (EI): m/z calcd for C10H18O: 154.13522; found: 154.13513.
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For Cu-catalyzed processes, see:
For Rh, see:
For α-alkylidene cyclopentanones, see:
For α-alkylidene cyclohexanones, see:
Attempts to trap the transient enolate with allyl chloroformate to obtain a derivatizable allyl vinyl carbonate were unsuccessful. For recent leading references, see:
For seminal work on asymmetric conjugate addition–aldolisation–elimination sequence, see:
For previous racemic syntheses of analogous substrates, see: