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Synlett 2016; 27(02): 272-276
DOI: 10.1055/s-0035-1560721
DOI: 10.1055/s-0035-1560721
letter
Copper(I)-Catalyzed Diastereoselective Borylative Exo-Cyclization of Alkenyl Aryl Ketones
Further Information
Publication History
Received: 26 June 2015
Accepted after revision: 10 September 2015
Publication Date:
09 November 2015 (online)
Abstract
Copper(I)-catalyzed diastereoselective borylative exo-cyclization of alkenyl ketones with bis(pinacolato)diboron is reported. The reaction of alkenyl aryl ketones under a CuCl/Xantphos catalyst system provides four- or five-membered-ring syn-2-(borylmethyl)cycloalkanol derivatives in good yields with high syn selectivities. The utility of this method is demonstrated by further transformations of the cyclic products.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1560721.
- Supporting Information
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- 17 Typical Procedure for the Borylative Cyclization/Esterification of Aryl Alkenyl Ketones: CuCl (0.025 mmol) and (pin)B–B(pin) (0.60 mmol), Xantphos (0.025 mmol), t-BuOK (0.60 mmol) were placed in an oven-dried vial in a glove box. After the vial was removed from the glove box, DME (1.0 mL) was added to the vial and stirred for 30 min. Then, 1a (0.50 mmol) was added to the mixture at 30 °C. After the reaction was complete, the reaction mixture was cooled to 0 °C. After that, DMAP [0.05 mmol in THF (1 mL)] and i-Pr2NEt (0.52 mmol) were added to the mixture, and 4-(trifluoromethyl)benzoyl chloride (0.53 mmol) was added dropwise. After the reaction was complete, the reaction mixture was passed through a short florisil column eluting with Et2O. The crude material was purified by silica gel column chromatography to give syn-4a (129.7 mg, 0.282 mmol, 56% yield) as a white solid. 1H NMR (392 MHz, CDCl3): δ = 1.25 (s, 6 H), 1.26 (s, 6 H), 1.36 (dd, J = 10.0, 15.9 Hz, 1 H), 1.46 (dd, J = 6.3, 15.7 Hz, 1 H), 1.68–1.79 (m, 1 H), 2.06–2.16 (m, 1 H), 2.62–2.72 (m, 1 H), 2.80–2.91 (m, 1 H), 2.97–3.07 (m, 1 H), 7.21–7.28 (m, 1 H), 7.30–7.36 (m, 2 H), 7.47–7.51 (m, 2 H), 7.68 (d, J = 7.8 Hz, 2 H), 8.20 (d, J = 7.8 Hz, 2 H). 13C NMR (99 MHz, CDCl3): δ = 12.5 (br, BCH2), 23.0 (CH2), 24.80 (Me), 24.86 (Me), 30.2 (CH2), 44.0 (CH), 83.2 (C), 85.4 (C), 125.0 (q, J C–F = 273.8 Hz, C), 125.1 (CH), 125.2–152.4 (m, CH), 127.2 (CH), 128.3 (CH), 130.0 (CH), 134.22 (q, J C–F = 32.7 Hz, C), 134.28 (C), 143.1 (C), 163.8 (C). HRMS (ESI): m/z [M + Na]+ calcd for C25H28O4BF3Na: 482.19613; found: 482.19653.
- 18 Several derivatization methods were examined to improve the isolated yield, but these were not successful.
- 19 The cuprate-carbonyl π complex may be formed in this step; see: Bertz SH, Hardin RA, Heavey TJ, Ogle CA. Angew. Chem. Int. Ed. 2013; 52: 10250
For examples of palladium-catalyzed carboborations, see:
For examples of copper(I)-catalyzed borylative aldol reactions, see:
For examples of copper(I)-mediated carboboration of alkynes, see:
For examples of copper(I)-catalyzed intermolecular carboboration of C–C double bonds, see:
For transition-metal-free carboborations, see:
For carboboration with coorperative Cu/Pd catalysis, see:
For selected examples, see:
For copper(I)-catalyzed borylative cyclizations, see:
For selected examples, see:
For selected examples of stereoselective cyclobutanol synthesis from simple starting materials, see:
For examples containing syn-selective cyclobutanol synthesis from simple starting materials, see: