Synlett 2016; 27(20): 2836-2840
DOI: 10.1055/s-0036-1588883
letter
© Georg Thieme Verlag Stuttgart · New York

The Preparation and Reactivity of 2-Bromo-3-(tri-n-butylstannyl)-1-propene

David R. Williams*
,
Akshay A. Shah
,
Dawn A. Brooks
,
Nicolas Zorn
Weitere Informationen

Publikationsverlauf

Received: 13. Mai 2016

Accepted after revision: 25. August 2016

Publikationsdatum:
09. September 2016 (online)


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.

Supporting Information

 
  • References and Notes

  • 1 New address: A. A. Shah, Pfizer, Groton, CT, 06340, USA.
  • 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.
    • 4a For an example of sequential SE′ reactions, see: Williams DR, Claeboe CD, Liang B, Zorn N, Chow NS. C. Org. Lett. 2012; 14: 3866
    • 4b For an example of sequential cross coupling–carbocyclization reactions, see: Williams DR, Shah AA, Mazumder S, Baik M.-H. Chem. Sci. 2013; 4: 238

      Two illustrative examples of total syntheses are cited:
    • 5a Piers E, Gilbert M, Cook KL. Org. Lett. 2000; 2: 1407
    • 5b Martin DB. C, Vanderwal CD. J. Am. Chem. Soc. 2009; 131: 3472
  • 6 Williams DR, Meyer KG. J. Am. Chem. Soc. 2001; 123: 765

    • For related reagents described from our laboratory, see:
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    • 7b Williams DR, Morales-Ramos ÁI, Williams CM. Org. Lett. 2006; 8: 4393

      For a representative sampling of reports, featuring bifunctional allyl synthons, see:
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    • 10c The data for the product 2-bromo-3-(tributylstannyl)prop-1-ene is given as follows: 1H NMR (400 MHz, CDCl3): δ = 5.6 (1 H, m), 5.35 (1 H, m), 2.25 (2 H, s), 1.70–0.70 (27 H, m). The reported data of their product differs substantially with respect to the key vinylic and allylic hydrogen assignments of Figure 1.
    • 11a Williams DR, Brooks DA, Meyer KG, Clark MP. Tetrahedron Lett. 1998; 39: 7251
    • 11b Williams DR, Meyer KG, Shamim K, Patnaik S. Can. J. Chem. 2004; 82: 120

      For examples, see:
    • 12a Williams DR, Kiryanov AA, Emde U, Clark MP, Berliner MA, Reeves JT. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 12058
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    • 12c Williams DR, Brooks DA, Berliner MA. J. Am. Chem. Soc. 1999; 121: 4924
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    • 13b Williams DR, Atwater BA, Bawel SA, Ke P, Gutierrez O, Tantillo DJ. Org. Lett. 2014; 16: 468
  • 14 For a discussion in total synthesis: Williams DR, Plummer SV, Patnaik S. Tetrahedron 2011; 67: 5083
  • 15 For preparation of the corresponding 2-chloro-3-(tri-n-butylstannyl)-1-propene: Baldwin JE, Adlington RM, Lowe C, O’Neil IA, Sanders GL, Schofield CJ, Sweeney JB. Chem. Commun. 1988; 1030
  • 16 Still WC. J. Am. Chem. Soc. 1978; 100: 1481
  • 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.
  • 18 Darwish A, Chong JM. Synth. Commun. 2004; 34: 1885