[71092-51-8] · C8H16Sn · 2-Trimethylstannylmethyl-1,3-butadiene · (MW 230.95)
Physical Data: bp 77-78 °C/40 mmHg.
Analysis of Reagent Purity: 1H NMR d 0.07 (9H, s), 1.89 (2H, d, J = 1.0 Hz), 4.65-5.20 (4H, m), 6.33 (1H, dd, J = 10.0, J = 17.4 Hz); l
Solubility: sol common organic solvents but avoid hydroxylic solvents.
Purification: by distillation.
Preparative Methods: by the reaction of the Grignard reagent prepared from chloromethyltrimethylstannane and chloroprene in the presence of a catalytic amount of dichlorobis(diphenylphosphino)propanenickel(II) in 75% yield,2 analogous to the procedure employed for the preparation of 2-Trimethylsilylmethyl-1,3-butadiene.3 The reaction of Trimethylstannyllithium4 with a-bromoisoprene5 also gives 2-trimethylstannylmethyl-1,3-butadiene in 70% yield.6
Handling, Storage, and Precautions: can be stored in a glass bottle under nitrogen. Organotin derivatives are known to be toxic. Therefore the reagents should be handled in a well-ventilated hood and contact with the skin and eyes should be avoided.
2-Trimethylstannylmethyl-1,3-butadiene undergoes Diels-Alder reactions with a variety of dienophiles in high yield (eqs 1 and 2). With unsymmetrical dienophiles, the
para products are obtained with higher selectivity than the reaction of the silicon analog (see 2-Trimethylsilylmethyl-1,3-butadiene).2
2-Trimethylstannylmethyl-1,3-butadiene enters the usual allylation reactions with carbonyl compounds in the presence of Boron Trifluoride Etherate (eq 3).7
Zinc Chloride-catalyzed reaction with Allyl Bromide results in the formation of allyl coupling products (eq 4).
Tohoku University, Sendai, Japan