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Tin for Organic Synthesis, 12. Synthesis of Aromatic and Olefinic Sodium Sulfonates by Electrophilic Destannylation with Trimethylsilyl Chlorosulfonate
Author(s) -
Niestroj Michael,
Lube Andreas,
Neumann Wilhelm P.
Publication year - 1995
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19951280609
Subject(s) - chemistry , trimethylsilyl , electrophile , hydrolysis , moiety , stereospecificity , tin , sodium , organic chemistry , reactivity (psychology) , medicinal chemistry , catalysis , alternative medicine , pathology , medicine
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‐alkenyl)dibutylstannanes ( 6a‐f ), or trialkylalkynylsta manes with trimethylsilyl chlorosulfonate ( 1 ) followed by hydrolysis with aqueous NaHCO 3 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 ).