Tetravinylstannane1

(CH2=CH)4Sn

[1112-56-7]  · C8H12Sn  · Tetravinylstannane  · (MW 226.91)

(vinyllithium precursor;2 vinyl nucleophile source for Stille coupling3)

Alternate Name: tetravinyltin.

Physical Data: bp 55-57 °C/17 mmHg, 67-70 °C/28 mmHg.

Solubility: sol common organic solvents; insol H2O.

Form Supplied in: available as a neat liquid. Major impurities are tin chlorides.

Preparative Methods: synthesized by the reaction of Vinylmagnesium Bromide with Tin(IV) Chloride in THF.4

Analysis of Reagent Purity: shows one spot in the TLC (hexane) and one peak in the GC. 1H NMR (C6D6) can also be informative.

Purification: commercial tetravinyltin is commonly used without further purification. Large quantities are purified by fractional distillation. Smaller amounts may be filtered through a plug of silica.

Handling, Storage, and Precautions: is an air and water stable oil. No unusual storage precautions are required. 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.

Vinyllithium.

The primary use of tetravinyltin is for the generation of vinyllithium. There are three common methods used to form vinyllithium. Treatment of a pentane solution of tetravinyltin with 2.0-2.5 equiv of n-Butyllithium in pentane initiates an exchange reaction which is driven by the precipitation of solid vinyllithium.2 Removal of solvent by syringe or filtration, followed by washing the vinyllithium and dissolution in Et2O, affords a solution of vinyllithium which is stable for long periods if stored under an inert atmosphere. An excess of tetravinyltin is employed because the exchange reaction will not proceed to completion.2 Ethereal vinyllithium solutions are stable for several months at 0 °C. A subsequent study using n-BuLi in hexane has shown that the vinyllithium solution can be contaminated with small amounts (<2%) of n-BuLi, n-hexyllithium, and Bu4Sn.5 Vinyllithium formed in this manner has been reacted with 1-chloro-2-methylcyclohexene to afford a substituted bicyclo[4.1.0]heptane (eq 1).4

Formation of solid vinyllithium can be avoided by treatment of an Et2O solution of tetravinyltin with 4 equiv of Phenyllithium.2 Removal of tetraphenyltin by filtration affords a solution of vinyllithium, which also contains LiBr from the PhLi preparation and trace levels of Ph4Sn (Ph4Sn is soluble in Et2O at 0.0010 g mL-1 at 20 °C). Vinyllithium generated in this manner has been reacted with a sulfonyldihydroisoxazole to afford the vinyldihydroisoxazole (eq 2).6 Use of Vinylmagnesium bromide afforded the product in low yield.

More recently, vinyllithium has been generated by the reaction of tetravinyltin with either 4 equiv of n-BuLi in THF7 or 4 equiv of Methyllithium in Et2O,8 obviating the need for filtration. Tetraalkylstannanes must not interfere with the ensuing steps. This approach has been used to generate lithium vinyltellurolate7 and vinylcyanocuprate.8 Reaction of vinyllithium generated in this manner with 1-naphthyloxazoline afforded, after acid quench, the trans-dihydronaphthalene (eq 3).9

Palladium-Mediated Cross-Coupling Reactions (Stille Reaction).

Tetravinyltin has occasionally been used as a nucleophile in palladium-mediated cross-coupling reactions with acid chlorides,10 bromo- and iodonucleosides (eq 4),11,12 and iodoglycals.13 Because only one vinyl equiv is transferred per tin, vinyltrimethyltin or Vinyltributylstannane are more commonly utilized in cross-coupling reactions.3

Protolytic and Halogenolytic Cleavage.

Tetravinyltin reacts once with I2 to give vinyl iodide and trivinyltin iodide.14 Similarly, reaction with aqueous HCl affords ethylene and trivinyltin chloride.15


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. Seyferth, D.; Weiner, M. A. JACS 1961, 83, 3583.
3. (a) Stille, J. K. AG(E) 1986, 25, 508. (b) Scott, W. J.; McMurry, J. E. ACR 1988, 21, 47.
4. Gassman, P. G.; Valcho, J. J.; Proehl, G. S.; Cooper, C. F. JACS 1980, 102, 6519.
5. Soderquist, J. A.; Rivera, I.; Negron, A. JOC 1989, 54, 4051.
6. Wade, P. A.; Bereznak, J. F.; Palfey, B. A.; Carroll, P. J.; Dailey, W. P. Sivasubramanian, S. JOC 1990, 55, 3045.
7. Silks, L. A., III; Odom, J. D.; Dunlap, R. B. SC 1991, 21, 1105.
8. (a) Nugent, W. A.; Hobbs, F. W., Jr. JOC 1986, 51, 3376. (b) Nugent, W. A.; Hobbs, F. W., Jr. OS 1988, 66, 52.
9. Meyers, A. I.; Lutomski, K. A.; Laucher, D. T 1988, 44, 3107.
10. Rich, D. H.; Singh, J.; Gardner, J. H. JOC 1983, 48, 432.
11. Herdewijn, P.; Kerremans, L.; Wigerinck, P.; Vandendriessche, F.; Van Aerschot, A. A. TL 1991, 32, 4397.
12. Mamos, P.; Van Aerschot, A. A.; Weyns, N. J.; Herdewijn, P. A. TL 1992, 33, 2413.
13. Friesen, R. W.; Loo, R. W. JOC 1991, 56, 4821.
14. Seyferth, D. JACS 1957, 79, 2133.
15. Cochran, J. C.; Bayer, S. C.; Bilbo, J. T.; Brown, M. S.; Colen, L. B.; Gasparini, F. J.; Goldsmith, D. W.; Jamin, M. D.; Nealy, K. A.; Resnick, C. T.; Schwartz, G. J.; Short, W. M.; Skarda, K. R.; Spring, J. P.; Strauss, W. L. OM 1982, 1, 586.

William J. Scott & Alessandro F. Moretto

Bayer Pharmaceuticals Division, West Haven, CT, USA



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