The hetero-Diels-Alder addition of sulfur dioxide: The pseudo-chair conformation of a 4,5-dialkylsultine
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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 ...
The energetics of dissocn. reactions of S82+ into stoichiometric mixts. of Sn+, n = 2-7, and Sm2+, m = 3, 4, 6, 10, were investigated by the B3PW91 method [6-311+G(3df)//6-311+G*] in the gas phase and in soln., with solvation energies calcd. using the SCIP ...
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 ...
The polydentate phosphinoamines 1,3-{(Ph2P)(2)N}(2)C6H4 and 2,6-{(Ph2P)(2)N}(2)C5H3N have been prepared in a single step from the reaction of the amines 1,3-(NH2)(2)C6H4 or 2,6-(NH2)(2)C5H3N with Ph2PCl in presence of Et3N (1:4:4 molar ratio) in CH2Cl2. Re ...
The reactivity of the iminodiphosphane C6H4(o-CN)N= PPh2-PPh2, which contains an N=P-P unit, has been investigated. Reaction with small molecules, [viz. H2O/O-2, H2O2, CH3OH, C6H4(o-CN)NH2] and elemental sulfur result in cleavage of the P-P bond to give am ...
The reactivity of (E)- and (Z)-1-fluorobuta-1,3-diene ((E)- and (Z)-11), 2-fluorobutadiene (12). (E)and (Z)-1-(fluoromethylidene)-2-methylidenecyclohexane ((E)- and (Z)-13) toward SO2 has been explored and compared with that of (Z)- and (E)-1-(fluoromethyl ...
A phosphino,oxazoline P,N-bidentate ligand, 4, contg. 3,5-di-tert-butylphenyl groups was prepd. In the Heck arylation of dihydrofuran, 4 affords higher ee's than either 2 or 3, the unsubstituted and m-dimethylphenyl analogs, resp. Several Pd(0) complexes 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 ...
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 ...
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 ...