17633-79-3Relevant academic research and scientific papers
Stereochemistry of the cyclization-rearrangement of (+)-copalyl diphosphate to (-)-abietadiene catalyzed by recombinant abietadiene synthase from Abies grandis
Ravn, Matthew M.,Coates, Robert M.,Flory, Janice E.,Peters, Reuben J.,Croteau, Rodney
, p. 573 - 576 (2007/10/03)
(equation presented) Syntheses and enzymatic cyclizations of 8α,hydroxy-17-nor copalyl diphosphate (8a), (15R)-[15-2H1] 8b, and (15R,17E)-[15-3H1,17-2H1] copalyl diphosphate ([2H,3H] 2) catalyzed by recombinant abietadiene synthase (rAS) gave 17-nor manoyl oxide (9a), (16E)-[16-2H1] 9b, and (15S,16R)-[16-2H1,16-3H1] abietadiene ([2H1,3H1] 4), respectively. These and other results indicate that conversion of CPP (2) to abietadiene (4) occurs by anti SN′ cyclization to a sandaracopimar-15-en-8-yl carbocation intermediate (13+, 13β-methyl)' followed by hydrogen transfer and methyl migration suprafacially on the si face of the vinyl group.
Ozonolysis of Derivatives of Labda-8(17),14-dien-13-ol (Manool) and Their Conversion into Large Ring Unsaturated Lactones
Grant, Peter K.,Lai, Chee Kong,Prasad, J. Siva,Yap, Tho Man
, p. 711 - 725 (2007/10/02)
Dehydration of the unstable hydroperoxy ethers (4) and (6) formed on ozonolysis of the manool derivatives (2) and (5) resulted in the formation of the ten-membered unsaturated lactones (11) and (12) in good yield.The results of an investigation into the nature of the hydroxyl group and its spatial relationship to the exocyclic double bond in lactone formation are reported for other manool derivatives.
SYNTHESIS OF LABDA-8(17),13(14)-DIENE-15,16-OLIDE AND 15,16-EPOXY-LABDA-8(17),13(16)-14-TRIENE AND THEIR REARRANGEMENT TO CLERODANE DERIVATIVES
Nakano, Tatsuhiko,Martin, Alfonso,Rojas, Anibal
, p. 1217 - 1219 (2007/10/02)
The title compounds 1b and 1c were synthesized from manool.On treatment with either trifluoroacetic acid or formic acid 1b provided in nearly 100percent yield 4a with a rearranged labdane skeleton.With sulfuric acid, however, 1b gave solely Δ8,9-isomer 5.Reduction of 4a with lithium diisobutylaluminium hydride afforded 4b.On treatment with sulfuric acid 4a reverted to 5.Rearrangement of the epoxide 6 with boron trifluoride-etherate led to a complex product mixture from wich no pure substance was obtained.
