Free accessResearch articleFirst published online 2015-4
Synthesis of Chiral Hexasubstituted Cyclohexanediol,a Key Intermediate for the Synthesis of Verticillol,from (+)-Dihydrocarvone;Attempted Cyclization to 12-Membered Carbocycle in Verticillol using RCM Reaction
A cyclohexane derivative with three chiral centers, a key intermediate for the synthesis of a diterpene verticillol, was prepared starting from (+)-dihydrocarvone. A further challenge to cyclize to a 12-membered carbocycle was attempted, although the products were dimeric derivatives presumably due to an undesirable conformation of the substrate.
ErdtmanH, NorinT, SumimotoM, MorrisonA. (1964) Verticillol, a novel type of conifer diterpene. Tetrahedron Letters, 5, 2349–2354.
2.
KarlssonB, PilottiAMSoderholmACNorinT, SundinS, SumimotoM. (1978) The structure and absolute configuration of verticillol, a macrocyclic diterpene alcohol from the wood of Sciadopitys verticillata Sieb. et Zucc. (Taxodiaceae). Tetrahedron, 54, 2349–2354.
3.
JinY, WilliamsDCCroteauR, CoatesRM. (2005) Taxadiene synthase-catalyzed cyclization of 6-fluorogeranylgeranyl diphosphate to 7-fluoroverticillenes. Journal of the American Chemical Society, 127, 7834–7842.
4.
NagashimaF, TamadaA, FujiiN, AsakawaY. (1997) Terpenoids from the Japanese liverworts Jackiella javanica and Jungermannia infusca. Phytochemistry, 46, 1203–1208.
5.
NagashimaF, WakayamaK, IokaY, AsakawaY. (2008) New ent-verticillane diterpenoids from the Japanese liverwort Jackiella javanica. Chemical & Pharmaceutical Bulletin, 56, 1184–1188.
6.
Cerda-Garcia-RojasCMGarcia-GutierrezHAHernandez-HernandezJDRoman-MartinLUJoseph-NathanP. (2007) Absolute configuration of verticillane diterpenoids by vibrational circular dichroism. Journal of Natural Products, 70, 1167–1172.
BegleyMJJacksonCBPattendenG. (1990) Total synthesis of verticillene. A biomimetic approach to the taxane family of alkaloids. Tetrahedron, 46, 4907–4924.
9.
McGrathNALeeCAArakiH, BrichacekM, NjardarsonJT. (2008) An efficient substrate-controlled approach towards hypoestoxide, a member of a family of diterpenoids natural products with an inside-out [9.3.1]bicyclic core. Angewandte Chemie, International Edition, 47, 9450–9453.
10.
AnetFAL, BournAJR. (1965) Nuclear magnetic resonance spectral assignments from nuclear Overhouser effects, Journal of the American Chemical Society, 87, 5250–5251.
GotoH, OsawaE. (1989) Corner flapping: A simple and fast algorithm for exhaustive generation of ring conformations. Journal of the American Chemical Society, 111, 8950–8951
13.
GotoH, OsawaE. (1993) An efficient algorithm for searching low-energy conformers of cyclic and acyclic molecules. Journal of the Chemical Society, Perkin Transactions 2, 187–198.
14.
ToriM, MizutaniR. (2010) Construction of eight-membered carbocycles with trisubstituted double bonds using ring closing metathesis reaction. Molecules, 15, 4242–4260.
