59060-59-2Relevant articles and documents
Long-Range Reactivity Modulations in Geranyl Chloride Derivatives
Reardon, Michael B.,Xu, Muyun,Tan, Qingzhe,Baumgartel, P. George,Augur, Danielle J.,Huo, Shuanghong,Jakobsche, Charles E.
, p. 10964 - 10974 (2016)
Derivatives of geraniol are versatile synthetic intermediates that are useful for synthesizing a variety of terpenoid natural products; however, the results presented herein show that subtle differences in the structures of functionalized geranyl chlorides can significantly impact their abilities to function as effective electrophiles in synthetic reactions. A series of focused kinetics experiments identify specific structure-activity relationships that illustrate the importance not only of steric bulk, but also of electronic effects from distant regions of the molecules that contribute to their overall levels of reactivity. Computational modeling suggests that destabilization of the reactant by filled-filled orbital mixing events in some, but not all, conformations may be a critical contributor to these important electronic effects.
Sesquiterpene Cyclizations inside the Hexameric Resorcinarene Capsule: Total Synthesis of δ-Selinene and Mechanistic Studies
Zhang, Qi,Tiefenbacher, Konrad
supporting information, p. 12688 - 12695 (2019/08/12)
The synthesis of terpene natural products remains a challenging task due to the enormous structural diversity in this class of compounds. Synthetic catalysts are unable to reproduce the tail-to-head terpene cyclization of cyclase enzymes, which create this diversity from just a few simple linear terpene substrates. Recently, supramolecular structures have emerged as promising enzyme mimetics. In the present study, the hexameric resorcinarene capsule was utilized as an artificial cyclase to catalyze the cyclization of sesquiterpenes. With the cyclization reaction as the key step, the first total synthesis of the sesquiterpene natural product δ-selinene was achieved. This represents the first total synthesis of a sesquiterpene natural product that is based on the cyclization of a linear terpene precursor inside a supramolecular catalyst. To elucidate the reaction mechanism, detailed kinetic studies and kinetic isotope measurements were performed. Surprisingly, the obtained kinetic data indicated that a rate-limiting encapsulation step is operational in the cyclization of sesquiterpenes.
Rearrangement of Linalool, Geraniol, and Nerol and Their Derivatives
Cori, Osvaldo,Chayet, Liliana,Perez, Luz Maria,Bunton, Clifford A.,Hachey, David
, p. 1310 - 1316 (2007/10/02)
Acid-catalyzed conversion of linalool into geraniol, nerol, and α-terpineol is slower than the corresponding reactions of geraniol and nerol, because the tertriary linalyl carbocation reverts to linalool rather than going forward to rearranged products.The linalyl carbocation does not lose its stereochemical identity, and oxygen exchange of linalool is faster than rearrangement or cyclization.Solvolyses of linalyl esters and chloride are faster than those of the geranyl and neryl derivatives.These solvolyses are different from acid heterolysis of linalool in that there is extensive racemization of linalool, but cyclization to α-terpineol goes with considerable retention of configuration.Participation by the 6,7-double bond controls the stereochemistry of linalool heterolysis and solvolysis of linalyl esters, but it does not markedly affect the reaction rates.
