102680-34-2Relevant articles and documents
Magnusson
, p. 2713 (1977)
Sex pheromone of pine sawflies: Enantioselective lipase catalysed transesterification of erythro-3,7-dimethylpentadecan-2-ol, diprionol
Lundh, Maren,Smitt, Olof,Hedenstroem, Erik
, p. 3277 - 3284 (2007/10/03)
(2S,3S,7R/S)-3,7-Dimethylpentadecan-2-ol (2S,3S,7R/S)-1 was prepared with less than 0.5% of (2R,3R,7R/S)-3,7-dimethylpentadecan-2-ol via Pseudomonas sp. (PSL) catalysed transesterification of a 1:1:1:1 mixture of the four erythro-3,7-dimethylpentadecan-2-ols and vinyl acetate in n-heptane at initial low water activity (a(w) 0.1). (2S,3S,7S)-3,7-Dimethylpentadecan-2-ol (Diprionol) is the precursor to the behaviourally active diprionyl acetate used by the female pine sawfly Neodiprion sertifer as a sexual pheromone. Several lipases, solvents and reaction conditions were tested, and the best results (enantiomeric ratio E = 110) were obtained with Pseudomonas sp. (PSL) and vinyl acetate in iso-octane at initial water activity a(w) 0.32. When using Candida rugosa (CRL, immobilised on polypropylene) as the catalyst in an esterification reaction with rac-4-methyl-dodecanoic acid and eicosanol at a(w) = 0.8 in cyclohexane a pronounced enantioselectivity was obtained (E = 19). Copyright (C) Elsevier Science Ltd.
Stereocontrolled Synthesis of Highly Oxygenated Acyclic Systems via the Enolate Claisen Rearrangement of O-Protected Allylic Glycolates
Gould, Thomas J.,Balestra, Michael,Wittman, Mark D.,Gary, Jill A.,Rossano, Lucius T.,Kallmerten, James
, p. 3889 - 3901 (2007/10/02)
Enolate Claisen rearrangement of E- and Z-allylic glycolates yields the syn- and anti-2-alkoxy-3-alkyl 4-enoates, respectively, in good yields (60-90percent) and with high internal diastereoselectivity.Incorporation of the glycolate Claisen procedure into an iterative sequence consisting of Claisen rearrangement and homologation by addition of vinyl nucleophiles results in the efficient, stereocontrolled generation of remotely functionalized, highly oxygenated acyclic systems.This strategy is demonstrated in stereoselective syntheses of pine sawfly pheromone 42 and tocopherol side-chain intermediate 30.