42217-00-5Relevant articles and documents
Application of a novel directing effect in an organocoppoer/orthoester reaction to the synthesis of deuterium labeled unsaturated esters
Shattuck, James C.,Svatos, Ales,Blazey, Charles M.,Meinwald, Jerrold
, p. 6803 - 6806 (1997)
Deuterium labeled methacrylates (5,6), tiglates (10,12), and senecioates (13,14,16,17), important for biosynthetic studies on the synthesis of carboxylic acids in carabid beetles, have been prepared using organocopper-alkyne coupling reactions. With 1,1,1,-triethoxypropyne as a coupling partner, a novel directing effect was observed; the 'branched' product was formed exclusively.
Self-assembled orthoester cryptands: Orthoester scope, post-functionalization, kinetic locking and tunable degradation kinetics
L?w, Henrik,Mena-Osteritz, Elena,Von Delius, Max
, p. 4785 - 4793 (2018/06/07)
Dynamic adaptability and biodegradability are key features of functional, 21st century host-guest systems. We have recently discovered a class of tripodal supramolecular hosts, in which two orthoesters act as constitutionally dynamic bridgeheads. Having previously demonstrated the adaptive nature of these hosts, we now report the synthesis and characterization-including eight solid state structures-of a diverse set of orthoester cages, which provides evidence for the broad scope of this new host class. With the same set of compounds, we demonstrated that the rates of orthoester exchange and hydrolysis can be tuned over a remarkably wide range, from rapid hydrolysis at pH 8 to nearly inert at pH 1, and that the Taft parameter of the orthoester substituent allows an adequate prediction of the reaction kinetics. Moreover, the synthesis of an alkyne-capped cryptand enabled the post-functionalization of orthoester cryptands by Sonogashira and CuAAC "click" reactions. The methylation of the resulting triazole furnished a cryptate that was kinetically inert towards orthoester exchange and hydrolysis at pH > 1, which is equivalent to the "turnoff" of constitutionally dynamic imines by means of reduction. These findings indicate that orthoester cages may be more broadly useful than anticipated, e.g. as drug delivery agents with precisely tunable biodegradability or, thanks to the kinetic locking strategy, as ion sensors.
Practical synthesis of functionalized terminal alkynes, 3,3,3-triethoxypropyne and ketal protected prop-2-ynones
Karanfil, Abdullah,Eskici, Mustafa
, p. 2342 - 2351 (2017/12/12)
Practical and economical synthesis of synthetically valuable 3,3,3-triethoxypropyne, ketal protected phenyl and methyl substituents prop-2-ynones is described. Bromination and subsequent 18-crown-6 catalyzed elimination of triethylorthoacrylate and ketal
