62107-46-4Relevant academic research and scientific papers
Biomimetic synthesis of acid-sensitive (-)- and (+)-caparrapi oxides, (-)- and (+)-8-epicaparrapi oxides, and (+)-dysifragin induced by artificial cyclases
Uyanik, Muhammet,Ishihara, Kazuaki,Yamamoto, Hisashi
, p. 5055 - 5065 (2005)
Asymmetric total syntheses of acid-sensitive (-)- and (+)-caparrapi oxides (1) and (+)-8-epicaparrapi oxide (2) from farnesol (10) are achieved using Sharpless-Katsuki epoxidation and Lewis acid-assisted chiral Bronsted acid (chiral LBA)-induced polyene cyclization as key steps. The relative configuration of (+)-dysifragin (4) is determined by a single-crystal X-ray diffraction and its total synthesis is accomplished by the diastereoselective epoxidation of (+)-1. Furthermore, (-)-1 can be directly synthesized from (S)-nerolidol (3) and (R)-LBA with 88% ds by reagent control, which overcame substrate control, while (-)-2 is obtained from (R)-3 and (R)-LBA with >99% ds by the double asymmetric induction.
Cyclization and Rearrangements of Farnesol and Nerolidol Stereoisomers in Superacids
Polovinka, Marina P.,Korchagina, Dina V.,Gatilov Yurii V.,Bagrianskaya Irina Yu.,Barkhash, Vladimir A.,et al.
, p. 1509 - 1517 (2007/10/02)
Acid-catalyzed cyclization of 2,3-trans- and 2,3-cis-farnesol proceeds regioselectively and stereospecifically, yielding drimenol and epi-drimenol, respectively.The trans and cis isomers of nerolidol undergo carbo- and heterocyclization reactions.The trans isomer gives tricyclic caged hydrocarbons with new skeletal types, while the rearrangements of the cis isomer produce derivatives of 2-oxabicyclodecane.The ICAR computer program was used to derive reasonable mechanisms for the acid-catalyzed transformations of nerolidol, and the probability of the mechanisms was evaluated by the molecular mechanics method.
CYCLIZATION OF ACYCLIC ISOPRENOIDS V REARRANGEMENT OF STEREOISOMERIC FARNESOLS AND NEROLIDOLS IN SUPERACIDS
Polovinka, M. P.,Unzur, N. D.,Perutskii, V. B.,Korchagina, D. V.,Gatilov, Yu. V.,et al.
, p. 1871 - 1885 (2007/10/02)
The cyclization of 2,3-trans- and -cis-farnesols in superacids is structurally selective and stereospecific, giving drimenol and epidrimenol respectively.Depending on the reaction conditions, trans- and cis-nerolidols undergo carbo- or hetero-cyclization, to give in the first case tricyclic bridged hydrocarbons with a novel skeleton, and in the second case a 2-oxabicyclodecane.
Stereoselective Olefin Cyclization Mediated by the Selenyl Group; Direct Formation of a Selenyl Caparrapi Oxide
Kametani, Tetsuji,Kurobe, Hiroshi,Nemoto, Hideo,Fukumoto, Keiichiro
, p. 1085 - 1088 (2007/10/02)
By acid-catalysed cyclization of 10-phenylseleno-3,7,11-trimethyldodeca-1,6-diene-3,11-diol (1), 3β-phenylselenocaparrapi oxide (5) was obtained stereoselectively as a mixture with its C-8 epimer, together with 5-(1,5-dimethyl-1-phenylselenohex-4-enyl)-2-
STEREOSELECTIVE OLEFINIC CYCLIZATION ASSISTED BY THE SELENYL GROUP - BIOGENETIC-TYPE SYNTHESIS OF CAPARRAPI OXIDE
Kametani, Tetsuji,Fukumoto, Keiichiro,Kurobe, Hiroshi,Nemoto, Hideo
, p. 3653 - 3656 (2007/10/02)
The acid catalysed cyclization of β-hydroxy selenide (4), which was prepared from nerolidol (1) via the epoxide (3), was carried out to give bicyclic ether (5) directly which was further transformed into caparrapi oxide (6).
Brominative Cyclisation of Nerolidol and Geranyl-linalool
Kato, Tadahiro,Ishii, Koichi,Ichinose, Isao,Nakai, Yoko,Kumagai, Takashi
, p. 1106 - 1108 (2007/10/02)
(+)-Nerolidol was treated with 2,4,4,6-tetrabromocyclohexa-2,5-dienone to afford the brominative cyclisation products α- and β-snyderols and 3-bromocaparrapi oxide and its 8-epimer; (+/-)-geranyl-linalool gave the analogous tricyclic ethers.
