Vinyltributylstannane1

[7486-35-3]  · C14H30Sn  · Vinyltributylstannane  · (MW 317.15)

(vinyl nucleophile in palladium-mediated cross-coupling reactions;2 occasionally used as a vinyllithium precursor3)

Alternate Name: vinyltributyltin.

Physical Data: bp 104-106 °C/3.5 mmHg, 95 °C/1.5 mmHg; d 1.085 g cm-3.

Solubility: sol common organic solvents; insol H2O.

Form Supplied in: neat oil; widely available. Occasionally contaminated with small amounts of Bu3SnCl.

Analysis of Reagent Purity: the pure compound shows one nonpolar spot by TLC (hexane) and one peak in the GC. 1H NMR can also be useful.

Preparative Methods: conveniently prepared by the reaction of Vinylmagnesium Bromide with Tri-n-butylchlorostannane.4

Purification: large quantities of material are purified by fractional distillation. Small amounts may be filtered through a plug of silica.

Handling, Storage, and Precautions: is air- and water-stable; requires no special handling or storage. Organostannanes are toxic and should only be used in a well ventilated hood. All glassware should be rinsed in a KOH/EtOH bath during cleaning.

Palladium-Mediated Cross Coupling (the Stille Reaction).

Vinyltributyltin is commonly used as a nucleophile in palladium-mediated cross-coupling reactions with organic electrophiles.2 The electrophile may be a halide or a pseudohalide which contains an sp or sp2 carbon at or immediately adjacent to the electrophilic center. Halide reactivity varies in the order: I > Br >> Cl. Either Pd0 or PdII catalysts may be used to mediate the reaction, the latter being reduced in situ by excess stannane. Acid chlorides react with vinyltributyltin in the presence of Benzylchlorobis(triphenylphosphine)palladium(II) in HMPA or chloroform at 65 °C (eq 1).5 In the latter solvent, yields are lower but the workup is significantly easier. Often the introduction of air into the reaction accelerates cross coupling of acid chlorides. Imidoyl chlorides (eq 2)6 and vinyl halides also undergo Pd-mediated cross coupling (eqs 3 and 4).7,8 Coupling of aryl halides typically requires electron poor aromatics or aryl iodides (eq 5).9

Hegedus et al. report a case in which an iodide attached to an electron-rich alkene fails to couple under normal conditions.10 Treatment of the vinyl halide under Heck alkenation conditions in the absence of solvent gives a moderate yield of the desired product (eq 6).10 Use of weakly donating stabilizing ligands, such as tri(2-furyl)phosphine and triphenylarsine, accelerates transmetalation, allowing coupling under conditions more gentle than those required with normal palladium catalysts [Pd(PPh3)4, PdCl2(PPh3)2, etc.] (eq 7).11

A number of pseudohalides act as electrophiles in palladium-catalyzed cross couplings. Vinyl and aryl triflates couple with a wide variety of organostannanes in the presence of excess of Lithium Chloride (eq 8).12-14 Cross coupling with aryl triflates is more difficult that with vinyl triflates, typically requiring either a more nucleophilic catalyst [Dichloro[1,1-bis(diphenylphosphino)ferrocene]palladium(II), (dppf)PdCl2)] or higher temperatures (dioxane at 98 °C) (eq 9).15 Use of vinyl16 or phenyl17 fluorosulfonates allows lower cost at the expense of lower stability with respect to the analogous triflate (eq 10). Arenesulfonates have also been coupled with vinyltributyltin.18 However, the generality of this variation is not yet clear.

Other electrophiles which undergo cross coupling include hypervalent iodine compounds (eq 11)19 and aryl diazonium salts (eq 12).20 Coupling of aryl diazonium salts requires excess vinyltributyltin and 1 equiv of the catalyst to avoid significant byproduct formation.20 Carbonylative couplings can be achieved if cross coupling is conducted under 1-3 atm of Carbon Monoxide (eq 13).14 Vinyltributyltin has also been used in tandem Heck alkenation/Stille couplings, in which the stannane is reacted with an alkyne and an electrophile in the presence of Tetrakis(triphenylphosphine)palladium(0) (eq 14).21,22

Transmetalation.

Transmetalation from tin offers a facile synthesis of vinyl nucleophiles. Treatment of vinyltributyltin with Methyllithium affords methyltributyltin and Vinyllithium (eq 15).3 Similarly, treatment with higher order cuprates causes quantitative in situ formation of the vinylcuprate (eq 16).23 Vinyltributyltin will transfer a vinyl group in reactions with both trimethylchlorogermane and tetrachlorogermane.24 Transmetalation with trimethylchlorogermane requires the presence of a catalytic amount of Aluminum Chloride. Treatment of an excess of vinyltributyltin with 9-Bromo-9-borabicyclo[3.3.1]nonane affords 9-Vinyl-9-borabicyclo[3.3.1]nonane while avoiding the manipulation of air-sensitive compounds.25 Excess vinyltributyltin is necessary to remove adventitious protic acid, and a greater than usual amount of H2O2/NaOH is used during oxidative hydrolysis to allow for reaction with bromotributyltin. Iodosulfonylation of vinyltributyltin followed by elimination of HI (DBU) affords the vinyl sulfone (eq 17),26 which can subsequently be used in Diels-Alder reactions or can be lithiated.27


1. (a) Pereyre, M.; Quintard, J.-P.; Rahm, A. Tin in Organic Synthesis; Butterworths: London, 1987. (b) Davies, A. G.; Smith, P. J. In Comprehensive Organometallic Chemistry; Wilkinson, G., Ed.; Pergamon: Oxford, 1982; Chapter 11. (c) Ingham, R. K.; Rosenberg, S. D.; Gilman, H. CRV 1960, 60, 459.
2. (a) Stille, J. K. AG(E) 1986, 25, 508. (b) Scott, W. J.; McMurry, J. E. ACR 1988, 21, 47.
3. Robichaud, A. J.; Meyers, A. I. JOC 1991, 56, 2607.
4. Seyferth, D.; Stone, F. G. A. JACS 1957, 79, 515.
5. Stille, J. K.; Labadie, J. W.; Tueting, D. JOC 1983, 48, 4634.
6. Kosugi, M; Koshiba, M.; Atoh, A.; Sano, H.; Migita, T. BCJ 1986, 59, 677.
7. Forsyth, C. J.; Clardy, J. JACS 1988, 110, 5911.
8. Wender, P. A.; Tebbe, M. J. S 1991, 1089.
9. Marsais, F.; Pineau, P.; Nivolliers, F.; Mallet, M.; Turck, A.; Godard, A.; Queguiner, G. JOC 1992, 57, 565.
10. Hegedus, L. S.; Holden, M. S. JOC 1986, 51, 1171.
11. Farina, V.; Baker, S. R.; Benigni, D. A.; Sapino, C. TL 1988, 29, 5739.
12. Scott, W. J.; Stille, J. K. JACS 1986, 108, 3033.
13. Peña, M. R.; Stille, J. K. JACS 1989, 111, 5417.
14. Echavarren, A. M.; Stille, J. K. JACS 1988, 110, 1557.
15. Echavarren, A. M.; Stille, J. K. JACS 1987, 109, 5478.
16. Roth, G. P.; Sapino, C. TL 1991, 32, 4073.
17. Roth, G. P.; Fuller, C. E. JOC 1991, 56, 3493.
18. Badone, D.; Cecchi, R.; Guzzi, U. JOC 1992, 57, 6321.
19. Moriarty, R. M.; Epa, W. R. TL 1992, 33, 4095.
20. Kikukawa, K.; Kono, K.; Wada, F.; Matsuda, T. JOC 1983, 48, 1333.
21. Chatani, N.; Amishiro, N.; Murai, S. JACS 1991, 113, 7778.
22. Kosugi, M.; Tamura, H.; Sano, H.; Migita, T. TL 1989, 45, 961.
23. Behling, J. R.; Babiak, K. A.; Ng, J. S.; Campbell, A. L. JACS 1988, 110, 2641.
24. Mironov, V. F.; Nuridzhanyan, A. K. Metalloorg. Khim. 1992, 5, 705 (CA 1992, 117, 234 145n).
25. Singleton, D. A.; Martinez, J. P.; Ndip, G. M. JOC 1992, 57, 5768.
26. Rasset-Deloge, C.; Martinez-Fresneda, P.; Vaultier, M. BSF 1992, 129, 285.
27. Ochiai, M.; Ukita, T.; Fujita, E. TL 1983, 24, 4025.

William J. Scott & Alessandro F. Moretto

Bayer Pharmaceuticals Division, West Haven, CT, USA



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