Stille Coupling

The Stille Coupling is a versatile C-C bond forming reaction between stannanes and halides or pseudohalides, with very few limitations on the R-groups. Well-elaborated methods allow the preparation of different products from all of the combinations of halides and stannanes depicted below. The main drawback is the toxicity of the tin compounds used, and their low polarity, which makes them poorly soluble in water. Stannanes are stable, but boronic acids and their derivatives undergo much the same chemistry in what is known as the Suzuki Coupling. Improvements in the Suzuki Coupling may soon lead to the same versatility without the drawbacks of using tin compounds.

Convenient electrophiles and stannanes:

---

Mechanism of the Stille Coupling

Recent Literature

Stille Coupling Made Easier - The Synergic Effect of Copper(I) Salts and the Fluoride Ion
S. P. H. Mee, V. Lee, J. E. Baldwin, Angew. Chem. Int. Ed., 2004, 43, 1132-1136.

Efficient Stille Cross-Coupling Reaction Catalyzed by the Pd(OAc)₂/Dabco Catalytic System
J.-H. Li, Y. Liang, D.-P. Wang, W.-J. Liu, Y.-X. Xie, D.-L. Yin, J. Org. Chem., 2005, 70, 2832-2834.

Pd(PPh₃)₄-PEG 400 Catalyzed Protocol for the Atom-Efficient Stille Cross-Coupling Reaction of Organotin with Aryl Bromides
H. Huang, H. Jiang, K. Chen, H. Liu, J. Org. Chem., 2009, 74, 5599-5602.

Palladium/Imidazolium Salt Catalyzed Coupling of Aryl Halides with Hypervalent Organostannates
G. A. Grasa, S. P. Nolan, Org. Lett., 2001, 3, 119-122.

Stille Couplings Catalytic in Tin:  A "Sn-F" Approach
R. E. Maleczka, W. P. Gallagher, Org. Lett., 2001, 3, 4173-4176.

Highly chemoselective coupling of allenylstannanes with organic iodides promoted by Pd(PPh₃)₄/LiCl: an efficient method for the synthesis of substituted allenes
C.-W. Huang, M. Shanmugasundaram, H.-M. Chang, C.-H. Cheng, Tetrahedron, 2003, 59, 3635-3641.

Palladium-Catalyzed Coupling of Allylic Acetates with Aryl- and Vinylstannanes
L. Del Valle, J. K. Stille, L. S. Hegedus, J. Org. Chem, 1990, 55, 3019-3023.

Palladium-Catalyzed Chemoselective Cross-Coupling of Acyl Chlorides and Organostannanes
R. Lerebours, A. Camacho-Soto, C. Wolf, J. Org. Chem., 2005, 70, 8601-8604.

---

Selected Articles

Synthesis of Carotenoids and Retinoids: Novel Approaches involving the Stille Reaction as a Key Step