ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-8529-2012 Technical Note: Synthesis of isoprene atmospheric oxidation products: isomeric epoxydiols and the rearrangement products <i>cis</i>- and <i>trans</i>-3-methyl-3,4-dihydroxytetrahydrofuran Zhang Z. 1 Lin Y.-H. 1 Zhang H. 1 Surratt J. D. 1 Ball L. M. 1 Gold A. 1 Department of Environmental Sciences and Engineering, Gillings School of Global Public Health, The University of North Carolina at Chapel Hill, NC, 27599-7431, USA 21 09 2012 12 18 8529 8535 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/12/8529/2012/acp-12-8529-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/8529/2012/acp-12-8529-2012.pdf

Isoprene epoxydiol (IEPOX) isomers are key gas-phase intermediates of isoprene atmospheric oxidation. Secondary organic aerosols derived from such intermediates have important impacts on air quality and health. We report here convergent and unambiguous pathways developed for the synthesis of isomeric IEPOX species and the rearrangement products <i>cis</i>- and <i>trans</i>-3-methyl-3,4-dihydroxytetrahydrofuran in good yield. The availability of such compounds is necessary to expedite research on isoprene atmospheric oxidation mechanisms and subsequent aerosol formation as well as the toxicological properties of the aerosols.

 References Adam, W. and Nestler, B.: Direct epoxy hydroxylation of hydroperoxy homoallylic alcohols: multidentate oxygen donor and oxygen acceptor substrates in titanium(IV)-catalyzed epoxidations, J. Am. Chem. Soc., 115, 7226–7231, 1993. Adam, W., Peters, K., and Renz, M.: Titanium-catalyzed diastereoselective epoxidations of ene diols and allylic alcohols with beta-hydroperoxy alcohols as novel oxygen donors, J. Org. Chem., 62, 3183–3189, 1997. Brill, W. F. and Indictor, N.: Reactions of $t$-butyl hydroperoxide with olefins, J. Org. Chem., 29, 710–713, 1964. Carlton, A. G., Wiedinmyer, C., and Kroll, J. H.: A review of Secondary Organic Aerosol (SOA) formation from isoprene, Atmos. Chem. Phys., 9, 4987–5005, http://dx.doi.org/10.5194/acp-9-4987-2009doi:10.5194/acp-9-4987-2009, 2009. Chan, M. N., Surratt, J. D., Claeys, M., Edgerton, E. S., Tanner, R. L., Shaw, S. L., Zheng, M., Knipping, E. M., Eddingsaas, N. C., Wennberg, P. O., and Seinfeld, J. H.: Characterization and quantification of isoprene-derived epoxydiols in ambient aerosol in the southeastern United States, Environ. Sci. Technol., 44, 4590–4596, 2010. Chiappe, C., De Rubertis, A., Tinagli, V., Amato, G., and Gervasi, P. G.: Stereochemical course of the biotransformation of isoprene monoepoxides and of the corresponding diols with liver microsomes from control and induced rats, Chem. Res. Toxicol., 13, 831–838, 2000. Claeys, M., Graham, B., Vas, G., Wang, W., Vermeylen, R., Pashynska, V., Cafmeyer, J., Guyon, P., Andreae, M. O., Artaxo, P., and Maenhaut, W.: Formation of secondary organic aerosols through photooxidation of isoprene, Science, 303, 1173–1176, 2004. Cole-Filipiak, N. C., O'Connor, A. E., and Elrod, M. J.: Kinetics of the hydrolysis of atmospherically relevant isoprene-derived hydroxy epoxides, Environ. Sci. Technol. 44, 6718–6723, 2010. Diekman, J., Thomson, J. B., and Djerassi, C.: Mass spectrometry in structural and stereochemical problems. CLV. Electron impact induced fragmentations and rearrangements of some trimethylsilyl ethers of aliphatic glycols, and related compounds, J. Org. Chem., 33, 2271–2284, 1968. Duvold, T., Cali, P., Bravo, J.-M., and Rohmer, M.: Incorporation of 2-C-methyl-D-erythritol, a putative isoprenoid precursor in the mevalonate-independent pathway, into ubiquinone and menaqunone of Escherichia coli, Tetrahedron Lett., 38, 6181–6184, 1997. Eddingsaas, N. C., VanderVelde D. G., and Wennberg, P. O.: Kinetics and products of the acid-catalyzed ring-opening of atmospherically relevant butyl epoxy alcohols, J. Phys. Chem. A, 114, 8106–8113, 2010. Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, http://dx.doi.org/10.5194/acp-6-3181-2006doi:10.5194/acp-6-3181-2006, 2006. Harwood, L. M., Casy, G., and Sherlock, J.: A simple laboratory procedure for preparation of (1-methylethenyl)oxirane (3,4-epoxyisoprene), Synthetic. Commun., 20, 1287–1291, 1990. Indictor, N. and Brill, W. F.: Metal Acetylacetonate catalyzed epoxidation of olefins with t-butyl hydroperoxide, J. Org. Chem., 30, 2074–2075, 1965. Khomenko, T. M., Tatarova, L. E., Korchagina, D. V., and Barkhash, V. A.: Rearrangements of epoxides of linalool and nerolidyl acetate in acid media, Russ. J. Org. Chem., 38, 498–506, 2002. Lin, Y.-H., Zhang, Z., Docherty, K. S., Zhang, H., Budisulistiorini, S. H., Rubitschun, C. L., Shaw, S., Knipping, E., Edgerton, E. S., Kleindienst, T. E., Gold, A., and Surratt, J. D.: Isoprene epoxydiols as precursors to secondary organic aerosol formation: acid-catalyzed reactive uptake studies with authentic standards, Environ. Sci. Technol., 46, 250–258, 2012. Matsumoto, M., Dobashi, S., Kuroda, K., and Kondo, K.: Sensitized photo-oxygenation of acyclic conjugated dienes, Tetrahedron, 41, 2147–2154, 1985. Morales, C. P., Catalan, J., Domingo, V., Delgado, J. A. G., Dobado, J. A., Herrador, M. M., del Moral, J. F. Q., and Barrero, A. F.: Protecting-group-free synthesis of chokols, J. Org. Chem., 76, 2494–2501, 2011. Paulot, F., Crounse J. D., Kjaergaard, H. G., Kürten, A., St Clair, J. M., Seinfeld, J. H., and Wennberg, P. O.: Unexpected epoxide formation in the gas-phase photooxidation of isoprene, Science, 325, 730–733, 2009. Pierce, A. E.: Silylation of organic compounds, Pierce Chemical Co., Rockford, 7–26, 1968. Pope III, C. A. and Dockery, D. W.: Health effects of fine particulate air pollution: lines that connect, J. Air Waste Manage., 56, 709–742, 2006. Rasmussen, K. G., Thomsen, D. S., and Joergensen, K. A.: Regio- and enantio-selective catalytic epoxidation of conjugated dienes, J. Chem. Soc. Perk. T. (now Org. Biomol. Chem.), 16, 2009–2017, 1995. Robinson, T. V., Pedersen, D. S., Taylor, D. K., and Tiekink, E. R. T.: Dihydroxylation of 4-substituted 1,2-dioxines: a concise route to branched erythro sugars, J. Org. Chem., 74, 5093–5096, 2009. Sheng, M. N. and Zajacek, J. G.: Hydroperoxide oxidations catalyzed by metals. III. Epoxidation of dienes and olefins with functional groups, J. Org. Chem., 35, 1839–1843, 1970. Surratt, J. D., Chan, A. W. H., Eddingsaas, N. C., Chan, M. N., Loza, C. L., Kwan, A. J., Hersey, S. P., Flagan, R. C., Wennberg, P. O., and Seinfeld, J. H.: Reactive intermediates revealed in secondary organic aerosol formation from isoprene, P. Natl. Acad. Sci. USA, 107, 6640–6645, 2010. Suzuki, S., Fujita, Y., Kobayashi, Y., and Sato, F.: A convenient preparative route to 1,2-epoxy-3-methyl-3-butene via ene-type chlorination, Synthetic. Commun., 16, 491–497, 1986. Wang, W., Kourtchev, I., Graham, B., Cafmeyer, J., Maenhaut, W., and Claeys, M.: Characterization of oxygenated derivatives of isoprene related to 2-methyltetrols in Amazonian aerosols using trimethylsilylation and gas chromatography/ion trap mass spectrometry, Rapid Commun. Mass Sp., 19, 1343–1351, 2005. Welzel, P., Böttger, D., Heinz, U., Said, A. H., Fischer, A., and Adams, E. A.: synthesis of moenocinol from isoprenoid precursors, Pure Appl. Chem., 59, 385–392, 1987.