Sugar allylic alcohols of the general formula Sug-CH=CH-CH2OH are easily converted into the allyltin derivatives Sug-CH=CH-CH2SnBu3 (7) by conversion into xanthate followed by its thermal rearrangement and subsequent SR2' reaction of resulting thiocarbonate with tri-n-butyltin hydride. Allyltin derivatives 7 undergo a controlled rearrangement with zinc chloride to dienoaldehydes CH2=CH-CH=CH-CH(OR)3CHO with the trans geometry across the internal double bond (3-E). Dienoaldehydes 3-E react with the C2-Wittig-type reagents [phosphoranes: Ph3P=CH-COR or phosphonates: (MeO)2P(O)CH2COR] to afford trienes 18 [CH2=CH-CH=CH-CH(OR)3CH=CH-C(O)-R), which undergo the intramolecular Diels-Alder reaction to give optically pure highly oxygenated bicyclo[4.3.0]indene derivatives 5 with the trans junction between the five and six-membered rings. Alternatively, the dienoaldehyde 3-E can be converted into - regioisomeric to 18 - triene 24 [CH2=CH-CH=CH-CH(OR)3C(O)-CH=CH-R], cyclization of which furnish optically pure bicyclo[4.4.0]decane derivatives 4 with the cis junction between both six-membered rings. On the other hand, sugar allylic bromides react with with tri-n-butyltin cuprate to afford a mixture of the primary and secondary allyltin derivatives [Sug-CH=CH-CH2SnBu3 (7) and [Sug-CH(SnBu3)-CH=CH2] (15) respectively]. Both isomers 7 and 15 might be converted into the trans dienoaldehyde 3-E by action of ZnCl2. However, thermal behavior of these regioisomers is different. The primary derivative 7 is stable up to at least 170 °C, while the secondary one (15) undergoes elimination of the tributylstannyl moiety already at 140 °C (boiling xylene) to afford dienoaldehyde with the cis-geometry across the internal double bond (3-Z). Such aldehyde was used for the preparation of - isomeric to 5 - derivative of bicyclo[4.3.0]indene with the cis-configuration between both rings (23). The stereochemistry of all these cyclizations might be rationalized assuming the endo-transition states of the intramolecular Diels-Alder reactions. Mechanism of the rearrangement of sugar allyltin derivatives 7 and 15 to unsaturated aldehydes 3-E and 3-Z is discussed.
Jak w sztuce zdobycie nagrody lub wyróżnienia toruje artście drogę do kariery, tak w dziedzinie wytwarzania produktów ich nagradzanie na wystawach czy targach przyciąga uwagę fachowców i inwestorów. Tak też stało się z udanym wyrobem firmy Computers&Control S.C. wyróżnionym na resortowych, prestiżowych imprezach wystawienniczych, a prezentowanym również na łamach AEE przez jego użytkownika. Właśnie opinia nabywcy urządzenia o jego eksploatacji jest najlepszą rekomendacją producenta, a potencjalnym nabywcom produktu staje się przydatna w podejmowaniu decyzji zakupu.