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Synlett 2016; 27(20): 2836-2840
DOI: 10.1055/s-0036-1588883
DOI: 10.1055/s-0036-1588883
letter
The Preparation and Reactivity of 2-Bromo-3-(tri-n-butylstannyl)-1-propene
Weitere Informationen
Publikationsverlauf
Received: 13. Mai 2016
Accepted after revision: 25. August 2016
Publikationsdatum:
09. September 2016 (online)
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Abstract
The preparation of 2-bromo-3-(tri-n-butylstannyl)-1-propene is described. This study characterizes the reactivity of 2-bromo-3-(tri-n-butylstannyl)-1-propene in SE′ reactions with aldehydes and includes a survey of radical reactions of 2-bromo-3-(tri-n-butylstannyl)-1-propene with α-bromocarbonyl compounds for C-alkylation.
Key words
organostannane preparation - bifunctional reagent - SE′ reactions - radical reaction - alkenyl bromidesSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1588883.
- Supporting Information
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References and Notes
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- 2 New address: D. A. Brooks, Eli Lilly & Company, Indianapolis, IN 46285, USA.
- 3 New address: N. Zorn, F. Hoffmann-La Roche AG, 4070 Basel, Switzerland.
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- 17 The allylic alcohol 2-bromo-1-propen-3-ol (10.6 g, 64.3 mmol) was dissolved in CH2Cl2 at 0 °C, and Et3N (10.3 mL, 73.9 mmol) was added under inert atmosphere. After stirring for 5 min, methanesulfonyl chloride (5.72 mL, 73.9 mL) was added dropwise at 0 °C. The reaction mixture was allowed to warm to 22 °C with continued stirring over 2 h. TLC (20% EtOAc in hexanes) shows the production of a less polar mesylate and the disappearance of starting alcohol. The reaction mixture was concentrated under reduced pressure to approximately one-third of its volume, and the concentrate was diluted with Et2O (150 mL). The mixture was filtered through a pad of Celite® to remove the triethylammonium hydrochloride precipitate with the aid of additional quantities of Et2O. The filtrate was concentrated in vacuo to give the crude mesylate as a yellow oil with yields consistently in the 85–90% range. Vacuum distillation (1.4 mm Hg pressure) by Kugelrohr bulb-to-bulb transfer at an oven temperature of 60 °C afforded product as a colorless liquid which was judged to be >97% pure based on the 1H NMR and 13C NMR spectra of these samples. 1H NMR (400 MHz, CDCl3): δ = 6.08 (1 H), 5.78 (1 H), 4.81 (2 H), 3.09 (3 H). 13C NMR (400 MHz, CDCl3): δ = 124.1, 121.7, 72.3, 38.5). HRMS (CI): m/z calcd for C4H8BrO3S [M + H]+ 214.9372; found: 214.9372. This mesylate was directly utilized in the next step.
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Two illustrative examples of total syntheses are cited:
For related reagents described from our laboratory, see:
For a representative sampling of reports, featuring bifunctional allyl synthons, see:
For examples, see: