Tin for Organic Synthesis, 12. Synthesis of Aromatic and Olefinic Sodium Sulfonates by Electrophilic Destannylation with Trimethylsilyl Chlorosulfonate

✍ Scribed by Niestroj, Michael ;Lube, Andreas ;Neumann, Wilhelm P.

• Publisher: Wiley (John Wiley & Sons)
• Year: 1995
• Tongue: English
• Weight: 658 KB
• Volume: 128
• Category: Article
• ISSN: 0009-2940
• DOI: 10.1002/cber.19951280609

✦ Synopsis

A mild and effective method for the preparation of a variety of aromatic, olefinic, and acetylenic sodium sulfonates is described. The reaction of trialkylaryl-(2a-k) and -heteroarylstannanes (4a-d), bis-(1-alkeny1)dibutylstannanes (6a-f), or trialkylalkynylstannanes with trimethylsilyl chlorosulfonate (1) followed by hydrolysis with aqueous NaHC03 provides the sodium sulfonates in an ipso-specific and in the case of vinylic stannanes stereospecific manner. A comparison of the reactivity of stannylated and silylated olefinic compounds 13 and 14 underlines the greater leaving ability of the stannyl moiety. The in situ preparation of the stannanes makes it possible to apply the synthetic method to natural products such as N-substituted apocodeine (17).