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Synlett 2016; 27(01): 17-20
DOI: 10.1055/s-0035-1560504
DOI: 10.1055/s-0035-1560504
letter
Asymmetric Organocatalytic Synthesis of Cyclopentane γ-Nitroketones
Further Information
Publication History
Received: 14 September 2015
Accepted: 25 September 2015
Publication Date:
15 October 2015 (online)
![](https://www.thieme-connect.de/media/synlett/201601/lookinside/thumbnails/st-2015-d0726-l_10-1055_s-0035-1560504-1.jpg)
Dedicated to Professor Steven V. Ley CBE FRS on the occasion of his 70th birthday
Abstract
This paper describes the use of bifunctional thiourea catalysts in the intramolecular reaction of a nitronate with conjugated ketones to generate the corresponding γ-nitroketones. In contrast to our previous studies in this area, we obtained the cis-functionalized systems as the major diastereoisomers in good yields and reasonable selectivities.
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References and Notes
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- 8 Representative Procedure To a solution of (E)-8-nitro-1-phenyloct-3-en-2-one (1, 150 mg, 0.6 mmol) in MeCN (5 mL) was added catalyst I (60.1 mg, 20 mol%) in one portion. The resulting mixture was stirred at r.t. for 7 d, whereupon the solvent was removed under reduced pressure, and the residue was purified by column chromatography (Et2O–hexane, 1:3) to afford cis-1-(2-nitrocyclopentyl)-3-phenylpropan-2-one (2d) as a colorless oil (140 mg, 94%).
- 9 Analytical Data for Compound 2d The ee was determined by chiral HPLC analysis at 20 °C to be 65% {Chiralpak AD-H [0.46 cm × 25 cm]: t R1 = 32.7 min, t R2 = 39.2 min}. 1H NMR (400 MHz, CDCl3): δ = 1.45–1.48 (2 H, m, CH2CH2CHNO2), 1.65–1.68 (2 H, m, CH2CHRCHNO2), 2.10 (1 H, m, CHHCHNO2), 2.34 (1 H, m, CHHCHNO2), 2.48 [2 H, m, cpCH2C(O)], 2.70 (1 H, m, CHNO2CHR), 3.80 (2 H, s, CH2Ph), 5.04 (1 H, dt, J = 6.6, 2.2 Hz, CHNO2), 7.17–7.30 (5 H, m, ArH). IR: 1260, 2973, 1714, 1544, 1458 cm–1. HRMS: m/z calcd for C14H18O3N [MH+]: 248.1132; found: 248.1133.
- 10 CCDC 1406015 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
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