10575-06-1Relevant articles and documents
Gold-Catalyzed Cycloisomerization of Sulfur Ylides to Dihydrobenzothiepines
Knittl-Frank, Christian,Saridakis, Iakovos,Stephens, Thomas,Gomes, Rafael,Neuhaus, James,Misale, Antonio,Oost, Rik,Oppedisano, Alberto,Maulide, Nuno
, p. 10972 - 10975 (2020)
The metal-promoted nucleophilic addition of sulfur ylides to π-systems is a well-established reactivity. However, the driving force of such transformations, elimination of a sulfide moiety, entails stoichiometric byproducts making them unfavorable in terms of atom economy. In this work, a new take on sulfur ylide chemistry is reported, an atom-economical gold(I)-catalyzed synthesis of dihydrobenzo[b]thiepines. The reaction proceeds under mild conditions at room temperature.
Improved synthesis of C8-C20 segment of pectenotoxin-2
Fujiwara, Kenshu,Suzuki, Yuki,Koseki, Nao,Murata, Shun-Ichi,Murai, Akio,Kawai, Hidetoshi,Suzuki, Takanori
scheme or table, p. 5589 - 5592 (2011/11/07)
The C8-C20 segment of pectenotoxin-2 was efficiently synthesized in 16% overall yield in 22 steps from l-malic acid via an improved route.
Elimination and Addition Reactions. Part 41. Nucleophilic Eliminative Fission of Cyclopropanes: the Coiled Spring Effect of Ring Strain on Nucleofugality and its Evaluation
Hughes, Simon,Griffiths, Gwerydd,Stirling, Charles J. M.
, p. 1253 - 1264 (2007/10/02)
Rates have been measured of sulphonyl-activated eliminative ring fissions of a series of six cyclopropanes in which the leaving group is stabilised by alkoxycarbonyl, cyano, or sulphonyl groups.The measurements allow assignment of ranks (nucleofugalities) to carbon leaving groups in systems in which the connection to the leaving group is strained by incorporation in a cyclopropane ring.The values obtained are compered with those obtained for a unstrained (acyclic) analogues.Rank enhancements of about 9(log) units are obtained; these enhancements suggests that free energies of activation for leaving-group expulsion are reduced by about 53 kJmol-1, or about 46 percent of these excess of enthalpy of the strained ring, notwithstanding the small degree of ring fission in the transition structure.The effect of phenyl substitution at the leaving group suggests that cleavage of the ring is very little advanced in the transition structure, although this is variable with the nature of the leaving-group stabilisation.This is the first direct determination of the effect of strain on nucleofugality.