24190-34-9Relevant articles and documents
Preparation of oxocene terpenes. the first enantiospecific synthesis of cytotoxic arenaran A
Torres, Alejandro,Gutierrez, Pilar,Alvarez-Manzaneda, Ramón,Chahboun, Rachid,Alvarez-Manzaneda, Enrique
, p. 9836 - 9845 (2016)
The first syntheses of cytotoxic marine arenarans A and B starting from commercial (-)-sclareol are reported. The oxocene ring of the target compound is formed via ring-closing metathesis, a process that depends on certain structural requirements. The tra
Asymmetric Cation-Olefin Monocyclization by Engineered Squalene–Hopene Cyclases
Aeberli, Natalie,Berweger, Raphael,Bornscheuer, Uwe T.,Buller, Rebecca,Dossenbach, Sandro,Eichenberger, Michael,Eichhorn, Eric,Flachsmann, Felix,Hüppi, Sean,Hortencio, Lucas,Patsch, David,Voirol, Francis,Vollenweider, Sabine
, p. 26080 - 26086 (2021/09/20)
Squalene–hopene cyclases (SHCs) have great potential for the industrial synthesis of enantiopure cyclic terpenoids. A limitation of SHC catalysis has been the enzymes’ strict (S)-enantioselectivity at the stereocenter formed after the first cyclization step. To gain enantio-complementary access to valuable monocyclic terpenoids, an SHC-wild-type library including 18 novel homologs was set up. A previously not described SHC (AciSHC) was found to synthesize small amounts of monocyclic (R)-γ-dihydroionone from (E/Z)-geranylacetone. Using enzyme and process optimization, the conversion to the desired product was increased to 79 %. Notably, analyzed AciSHC variants could finely differentiate between the geometric geranylacetone isomers: While the (Z)-isomer yielded the desired monocyclic (R)-γ-dihydroionone (>99 % ee), the (E)-isomer was converted to the (S,S)-bicyclic ether (>95 % ee). Applying the knowledge gained from the observed stereodivergent and enantioselective transformations to an additional SHC-substrate pair, access to the complementary (S)-γ-dihydroionone (>99.9 % ee) could be obtained.
Ring a functionalization of terpenoids by the unusual Baeyer-Villiger rearrangement of aliphatic aldehydes
Barrero, Alejandro F.,Alvarez-Manzaneda,Alvarez-Manzaneda,Chahboun, Rachid,Mencses,Marta Aparicio
, p. 713 - 716 (2007/10/03)
A new methodology is described for transforming resinic acids into nor- alcohols and nor-olefins, via the Baeyer-Villiger rearrangement of the derived aldehyde. Based on this methodology 4-hydroxy-18-nor-abieta-8,11,13- trien-7-one and 18-nor-abieta-8,11,13-triene-4,7α-diol, two new terpenoids recently described, have been synthesized from abietic acid.