Competition between hetero-Diels-Alder and cheletropic additions of sulfur dioxide to 2-substituted buta-1,3-dienes. Synthesis of 2-(1-naphthyl)and 2-(2-naphthyl)buta-1,3-diene
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In the presence of sulfur dioxide and an acid promoter, (-)-(1E,3Z)-2-methyl-1-((1S)-1-phenyleth- oxy)penta-1,3-dien-3-yl isobutyrate reacts with (Z)-3-(trimethylsilyloxy)-pent-2-ene giving a silyl sulfinate intermediate that undergoes, in the presence of ...
Ring strain confers to the cyclopropane ring an exceptional reactivity. Nevertheless, activation of the cyclopropane ring is usually needed to allow ring-opening reactions under mild conditions. The introduction of one or several carbonyl functionalities o ...
Under appropriate conditions sulfur dioxide reacts with 1,3-dienes in the hetero-Diels-Alder fashion. In the case of 1-alkoxy-1,3-dienes the 6-alkoxy-3,6-dihydro-1,2-oxatiin-2-oxides (sultines) so-obtained can be ionized in the presence of Lewis or protic ...
The goal of this thesis was to open a new route to the synthesis of conjugated trienes using a new SO2-based C-C bond forming reactions developed in Lausanne. In addition, the potential of SO2 for applications in synthetic organic chemistry has been exploi ...
Natural polyketides show important biological activity. The inherent stereochemical complexity present in this class of molecules has captured the imagination of organic chemists. Their stereocontrolled, asymmetric total synthesis is a permanent and stimul ...
Sulphur dioxide reacts with 1-oxydienes generating zwitterions which are quenched by enoxysilanes to form substituted silyl alkenylsulfinates. These intermediates are desilylated with Bu4NF and the resulting sulfinates react with MeI giving the correspondi ...
2-Methylprop-2-ene-1-sulfonyl fluorides can be easily prepared via the ene reaction of methallylsilanes and SO2. In the presence of a base, aldehydes and 2-methylprop-2-ene-1-sulfonyl fluorides give 1.3-(E) and (Z)-dienes. Their (Z) --> (E) isomerization b ...
In the presence of a Lewis or protic acid and at low temperature, 1,3-dioxy-1,3-dienes add to sulfur dioxide generating zwitterionic intermediates that can react with carbon nucleophiles such as allylsilanes. After a retro-ene elimination of SO2, valuable ...
At low temperature, 1-alkoxy-1,3-dienes add to sulfur dioxide activated by a Lewis or protic acid generating zwitterionic intermediates that can be quenched by enoxysilanes. The resulting beta,gamma-unsaturated silyl sulfinates can be desilylated by 1:1 Pd ...
Even unsubstituted butadiene adds to sulfur dioxide in the hetero-Diels Alder mode more rapidly than in the chelotropic mode. The sultine can be observed in equilibrium with the diene and the sulfur dioxide only at low temperature and in the presence of CF ...