Synthesis, Table of Contents Synthesis 2019; 51(07): 1633-1642DOI: 10.1055/s-0037-1611367 paper © Georg Thieme Verlag Stuttgart · New York Oxidative Dearomatization and Sigmatropic 1,3-Acyl Shift in Excited State: Aromatics to Embellished cis-Hydrindanes Raghaba Sahu a Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400076, India Email: vks@chem.iitb.ac.in , Vishwakarma Singh* a Department of Chemistry, Indian Institute of Technology Bombay, Mumbai 400076, India Email: vks@chem.iitb.ac.in b Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Bhopal 462066, India › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract A stereoselective synthetic route to embellished cis-hydrindanes from simple aromatic precursors is described. Oxidative dearomatization, ring expansion, and photochemical 1,3-acyl shift are the key features of our approach. Oxidative dearomatization of o-(hydroxymethyl)phenols followed by π4s + π2s cycloaddition furnishes bicyclo[2.2.2]octanes with contiguous keto epoxide groups, which upon ring expansion lead to bicyclo[3.2.2]nonanes endowed with a β,γ-enone chromophore. Unbridging of bicyclo[3.2.2]nonanes upon singlet excitation furnishes embellished cis-hydrindanes. Key words Key wordsoxidative dearomatization - cycloaddition - 1,3-acyl shift - cis-hydrindanes - ring expansion Full Text References References 1a Silva LF. Jr. Synlett 2014; 25: 466 1b Fleming FF, Gudipati S. Eur. J. Org. Chem. 2008; 5365 1c Brocksom TJ, Coelho F, Depres J.-P, Greene AE, Freire de Lima ME, Hamelin O, Hartmann B, Kanazawa AM, Wang Y. J. Am. Chem. Soc. 2002; 124: 15313 1d Abe N, Onada R, Sirahata K, Tadahiro K, Woods MC, Kitahara Y, Ro K, Kurihara T. Tetrahedron Lett. 1968; 9: 1993 1e Toshima H, Nara S, Ichihara A. Biosci., Biotechnol., Biochem. 1997; 61: 752 ; and references therein 1f Schäfer A, Hiersemann M. Org. Lett. 2017; 19: 814 1g Rho J.-R, Lee H.-S, Sim CJ, Shin J. Tetrahedron 2002; 58: 9585 2a Schafer A, Kohler SC, Lohe M, Wiese M, Hiersemann M. J. Org. Chem. 2017; 82: 10504 ; and references therein 2b Handore KL, Seetharamsingh B, Reddy DS. J. Org. Chem. 2013; 78: 8149 2c Han Y, Zhu L, Gao Y, Lee C-S. Org. Lett. 2011; 13: 588 2d Findley TJ. K, Sucunza D, Miller LC, Helm MD, Helliwell M, Davies DT, Procter DJ. Org. Biomol. Chem. 2011; 9: 2433 ; and references therein 3a Ferraz HM. C, Vieira TO, Silva LF. Jr. Synthesis 2006; 2748 3b Fleming FF, Zhang Z, Wang Q, Steward OW. Org. Lett. 2002; 4: 2493 3c Minger TL, Phillips AJ. Tetrahedron Lett. 2002; 43: 5357 3d Mehta G, Reddy DS. J. Chem. Soc., Perkin Trans. 1 2001; 1153 4a Abd El-Gaber MK, Yasuda S, Iida E, Mukai C. Org. Lett. 2017; 19: 320 4b Tanimura S, Yokoshima S, Fukuamya T. Org. Lett. 2017; 19: 3684 4c Eddy NA, Ichalkaranje P. Molecules 2016; 21: 1358 5a Pouysegu L, Chassaing S, Dejugnac D, Lamidey A.-M, Miqueu K, Sotiropoulos J.-M, Quideau S. Angew. Chem. Int. Ed. 2008; 47: 3552 5b Luo S.-Y, Jang Y.-J, Liu J.-Y, Chu C.-S, Liao C.-C, Hung S.-C. Angew. Chem. Int. Ed. 2008; 47: 8082 5c Pouysegu L, Deffieux D, Quideau S. Tetrahedron 2010; 66: 2235 5d Roche SP, Porco JA. Jr. Angew. Chem. Int. Ed. 2011; 50: 4068 5e Yang Q, Njardarson JT, Draghici C, Li F. Angew. Chem. Int. Ed. 2013; 52: 8648 6a Magdziak D, Meek SJ, Pettus TR. R. Chem. Rev. 2004; 104: 1383 6b Liao C.-C, Peddinti RK. Acc. Chem. Res. 2002; 35: 856 6c Mehta G, Maity P. Tetrahedron Lett. 2008; 49: 318 6d Krawczuk PJ, Schone N, Baran PS. Org. Lett. 2009; 11: 4774 6e Gong J, Lin G, Sun W, Li C. -C, Yang Z. J. Am. Chem. Soc. 2010; 132: 16745 6f Constantin M.-A, Conrad J, Merisor E, Koschorreck K, Urlacher VB, Beifuss U. J. Org. Chem. 2012; 77: 4528 7a Singh V. Acc. Chem. Res. 1999; 32: 324 7b Singh V, Pal S, Mobin SM. J. Org. Chem. 2006; 71: 3014 7c Singh V, Chandra G, Mobin SM. Synthesis 2008; 2719 7d Singh V, Sahu PK, Sahu BC, Mobin SM. J. Org. Chem. 2009; 74: 6092 7e Singh V, Sahu BC, Bansal V, Mobin SM. Org. Biomol. Chem. 2010; 8: 4472 7f Singh V. Synlett 2013; 24: 2641 8a Aga M, Okada K, Oda M. Tetrahedron Lett. 1986; 27: 5653 8b Papadopoulos M, Jenner G. Tetrahedron Lett. 1985; 26: 3335 8c Kurtz DW, Johnson RP. J. Chem. Educ. 1989; 66: 873 9a Li P, Yamamoto H. J. Am. Chem. Soc. 2009; 131: 16628 9b Shireman BT, Miller MJ. J. Org. Chem. 2001; 66: 4809 9c Dahnke KR, Paquette LA. J. Org. Chem. 1994; 59: 885 9d Li Z.-H, Mori A, Takeshita H. Bull. Chem. Soc. Jpn. 1990; 63: 3713 10a Sahu R, Singh V. J. Org. Chem. 2017; 82: 6268 10b Singh V, Porinchu M, Vedantham P, Sahu PK. Org. Synth. 2005; 81: 171 11a Adler E, Brasen S, Miyake H. Acta Chem. Scand. 1971; 25: 2055 11b Adler E, Holmberg K. Acta Chem. Scand., Ser. B 1974; 28: 465 12 Ngo K.-S, Brown GD. Tetrahedron 1999; 55: 15099 13a Schuster DI. In Rearrangement in Ground and Excited States . Vol. 3. de Mayo P. Academic; New York: 1980: 167 13b Demuth M, Schaffner K. Angew. Chem. Int. Ed. 1982; 21: 820 13c Zimmerman HE, Armesto D. Chem. Rev. 1996; 96: 3065 14a Armesto D, Ortiz MJ, Romano S, Agarrabeitia AR, Gallega MG, Ramos A. In CRC Handbook of Organic Photochemistry and Photobiology . Horspool WM, Lenci F. CRC Press; Boca Raton, FL: 2004. Chap. 95 14b Singh V. In CRC Handbook Organic Photochemistry and Photobiology . Horspool WM, Lenci F. CRC; Boca Raton, FL: 2004. Chaps. 78 and 79 14c Banwell MG, Bon DJ.-Y. D. In Molecular Rearrangements in Organic Synthesis . Rojas CM. Wiley; Hoboken, NJ: 2016. Chap. 9 15a Goodell JR, Poole JL, Beeler AB, Aube J, Porco JA. Jr. J. Org. Chem. 2011; 76: 9792 15b Bach T, Hehn JP. Angew. Chem. Int. Ed. 2011; 50: 1000 16a Lan P, Banwell MG, Willis AC. Org. Lett. 2015; 17: 166 16b Wang C.-C, Ku Y.-C, Chuang GJ. J. Org. Chem. 2015; 80: 10979 16c Yan Q, Bolte B, Bai Y, Banwell MG, Willis AC, Carr PD. J. Org. Chem. 2017; 82: 8008 17a Uyehara T, Furuta T, Kabasawa Y, Yamada J.-I, Kato T. J. Chem. Soc., Chem. Commun. 1986; 539 17b Uyehara T, Kabasawa Y, Kato T, Furuta T. Tetrahedron Lett. 1985; 26: 2343 Supplementary Material Supplementary Material Supporting Information
