This review is a detailed account of authors’ work in the field of biomimetic cyclization of geraniol-like dienes. The very high regio- and enantioselectivity achieved made these elegant reactions a viable tool for the synthesis of monocyclic building blocks used in the synthesis of valued terpenoids, like the precious aroma and perfume constituents’ ionones and irones.
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EschenmoserA., ArigoniD. (2005) Revisited after 50 Years: The =Stereochemical Interpretation of the Biogenetic Isoprene Rule for the Triterpenes’. Helvetica Chimica Acta, 88, 3011–3050.
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NicolaouK.C., EdmonsD.J., BulgerP.G. (2006) Cascade reactions in total synthesis. Angewandte Chemie International Edition, 45, 7134–7186 and references therein.
10.
BrunoldiE., LupariaM., PortaA., ZanoniG., VidariG. (2006) Biomimetic cyclizations of functionalized isoprenoid polyenes: a cornucopia of synthetic opportunities. Current Organic Chemistry, 10, 2259–2282.
11.
AbeI. (2007) Enzymatic synthesis of cyclic triterpenes. Natural Product Reports, 24, 1311–1331 and references cited therein.
12.
AlcarazL., HarnettJ.J., MioskowskiC., Le GallT., ShinD.S., FalkJ.R. (1995) Taxol Total Synthesis: Preparation of a Chiral Ring A Moiety via Biomimetic Cyclization and Evaluation of a Tandem Nitrile Oxide Strategy for Rings B/C. Journal of Organic Chemistry, 60, 7209–7214 and references cited therein.
13.
BarreroA.F., Alvarez-ManzanedaE.J., Linares PalominoP. (1994) Synthesis of (±)-karahana ether and karahanaenone by selective cyclization of 6,7-epoxygeranyl acetate. Tetrahedron, 50, 13239–13250.
14.
KulcitkiV., (2007) A biomimetic approach to some specifically functionalized cyclic terpenoids. Acta Biochimica Polonica, 54, 679–693 and references cited therein.
15.
VidariG., BeszantS., El MerabetJ., BovolentaM., ZanoniG. (2002) FeCl3 and ZrCl4 regiochemically controlled biomimetic-like cyclizations of simple isoprenoid epoxyolefins. Tetrahedron Letters, 43, 2687–2690.
16.
BovolentaM., CastronovoF., VadalàA., ZanoniG., VidariG. (2004) A simple and efficient highly enantioselective synthesis of α-ionone and α-damascone. Journal of Organic Chemistry, 69, 8959–8962.
17.
(a) VidariG., DapiaggiA., ZanoniG., GarlaschelliL. (1993) Asymmetric dihydroxylation of geranyl, neryl and trans, trans-farnesyl acetates. Tetrahedron Letters34, 6485–6488;(b) Corey EJ, Noe MC, Shieh WC. (1993) A short and convergent enantioselective synthesis of (3S)-2,3-oxidosqualene. Tetrahedron Letters, 34, 5995-5998.
18.
LupariaM., BoschettiP., PiccininiF., PortaA., ZanoniG., VidariG. (2008) Enantioselective synthesis and olfactory evaluation of 13-alkyl-substituted α-ionones. Chemistry and Biodiversity, 5, 1045–1057.
19.
VladP.F. (1993) Superacidic cyclization of terpenoids. Pure and Applied Chemistry, 65, 1329–1336.
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22.
DessD.H., MartinJ.C. (1991) A useful 12-I-5 triacetoxyperiodinane (the Dess-Martin periodinane) for the selective oxidation of primary or secondary alcohols and a variety of related 12-I-5 species. Journal of the American Chemical Society, 113, 7277–7287.
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(a) JuliaM., ParisJ.M. (1973) Syntheses a l'aide de sulfones v(+)- methode de synthese generale de doubles liaisons. Tetrahedron Letters, 14, 4833–4836;(b) Kocienski PJ, Lythgoe B, Waterhouse I. (1980) The influence of chain-branching on the steric outcome of some olefin-forming reactions. Journal Chemical Society, Perkin Transaction 1, 1045-1050.
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LupariaM., LegnaniL., PortaA., ZanoniG., TomaL., VidariG. (2009) Enantioselective synthesis and olfactory evaluation of bicyclic α- and γ-ionone derivatives: the 3D arrangement of key molecular features relevant to the violet odor of ionones. Journal of Organic Chemistry, 74, 7100–7110.
25.
BeszantS., GianniniE., ZanoniG., VidariG. (2002) Enantioselective synthesis of both enantiomers of γ-ionone, γ-damascone, karahana lactone and karahana ether. Tetrahedron: Asymmetry, 13, 1245–1255.
26.
BeszantS., GianniniE., ZanoniG., VidariG. (2003) Electrophilic cyclization of 1,6-dienes containing an allylsilane moiety – Enantioselective synthesis of cis- and trans-γ-irone. European Journal of Organic Chemistry, 3958–3968.
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LegnaniL., LupariaM., ZanoniG., TomaL., VidariG. (2008) A full conformational characterization of natural ionones and irones, as well as 13-alkyl-substituted α-ionones. European Journal of Organic Chemistry, 4755–4762.
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AltenbachH.J. (1991) Functional group transformations via allyl rearrangement. In Comprehensive Organic Synthesis. Vol. 6, TrostB.M., FlemingI., SemmelhackM.F. (Eds). Pergamon Press, Oxford, UK. 829–871.
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KocienskiP.J. (1979) Terminal olefins from the fluoride-induced elimination of β-silylsulfones. Tetrahedron Letters, 20, 2649–2650.
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(a) ArmstrongR.J., WeilerL. (1983) Stereoselective cyclization of epoxy allylsilanes. A synthesis of karahana ether. Canadian Journal of Chemistry, 61, 214–215;(b) Armstrong RJ, Weiler L. (1986) Synthesis of (±)-karahana ether and a (±)-labdadienoic acid by the electrophilic cyclization of epoxy allylsilanes. Canadian Journal of Chemistry, 64, 584-596.
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VidariG., LanfranchiG., MasciagaF., MoriggiJ.D. (1996) Enantioselective synthesis of γ-cyclohomocitral, pallescensone, and ancistrodial. Tetrahedron: Asymmetry, 7, 3009–3020.
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(a) BrennaE., DelmonteM., FugantiC., SerraS. (2001) Enzyme-mediated preparation of (+)- and (-)-β-irone and (+)- and (-)-cis-γ-irone from Irone alpha. Helvetica Chimica Acta, 84, 69–86;(b) Brenna E, Fuganti C, Ronzani S, Serra S. (2001) Enzyme-mediated syntheses of the enantiomers of γ-irones. Helvetica Chimica Acta, 84, 3650-3666.
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Schulte-ElteK.H., PamingleH., UijtterwaalP., SnowdenR.L. (1992) An alternative access to (±)-α-irones and (±)-β-irone via acid-mediated cyclization. Helvetica Chimica Acta, 75, 759–765 and references cited therein.
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MandaiT., NishikawaK., YamaguchiH., KawadaM., OteraJ. (1981) Total synthesis of ionones and irones from 2-(hydroxymethyl)-4-(phenylthio)-1-butene. Chemistry Letters, 473–474.
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MatsubaraS., NonakaT., OkudaY., KanemotoS., OshimaK., NozakiK. (1985) Retentive stereospecificity in deoxygenation of epoxides with tin-aluminum or silicon-aluminum reagents. Bulletin of the Chemical Society of Japan, 58, 1480–1483.
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(a) De BernardiM., GarlaschelliL., GattiG., VidariG., Vita FinziP. (1988) Fungal metabolites. XXII. The unprecedented structure of saponaceolide A, a cytotoxic C-30 terpenoid from Tricholoma saponaceum. Tetrahedron, 44, 235–240; (b) De Bernardi M, Garlaschelli L, Toma L, Vidari G, Vita Finzi P. (1991) Fungal metabolites. XXVI. The structure of saponaceolides B, C and D, new C-30 terpenoids from Tricholoma saponaceum. Tetrahedron, 47, 7109-7116.
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(a) FerezouJ.P., JuliaM. (1985) Biomimetic synthesis of bacterial C50 carotenoids decaprenoxanthin and c.p. 450. Tetrahedron, 41, 1277–1287;(b) Julia M, Schmitz C. (1986) Prenylation-cyclisation of geranyl acetate. Tetrahedron, 42, 2491-2500; (c) Ferezou JP, Julia M. (1990) Synthesis of bacterial C50 carotenoid sarcinaxanthin. Tetrahedron, 46, 475-486.
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