Unprecedented C-Methylation at the 2-Position of 2-Carboxy-4-Chromanones – A Case Study with the Corey–Chaykovsky Reagent

Abstract

An unprecedented C-methylation at the 2-position of 4-chromanone-2-carboxylates was achieved in good yield on treatment with dimethylsulfoxonium methylide. The reaction was performed with excellent chemo- as well as regioselectivity. It is the first synthetic report of alkylation at the 2-position of the chromanone framework through a very mild and simple approach. Such an uncommon behavioral pattern of the Corey–Chaykovsky reagent is justified by theoretical potential energy surface calculations.

Key words

4-chromanone-2-carboxylate - C-methylation - regioselectivity - dimethylsulfoxonium methylide - theoretical calculations

• References

• 1 Wittig G, Geissler G. Justus Liebigs Ann. Chem. 1953; 580: 44
• 2a Franzen V, Schmidt H.-J, Mertz C. Chem. Ber. 1961; 94: 2942
• 2b Franzen V, Driesen H.-E. Chem. Ber. 1963; 96: 1881
• 2c Corey EJ, Chaykovsky M. J. Am. Chem. Soc. 1965; 87: 1353
• 3a Trost BM, Melzin LS. Sulfur Ylides: Emerging Synthetic Intermediates. Vol. 31. Academic Press; New York: 1975
• 3b Bernardy F, Sizmadia G, Magini A. Organic Sulfur Chemistry. Elsevier; New York: 1985
• 4 Gololobov YG, Nesmeyanov AN, Iysenko VP, Boldeskul IE. Tetrahedron 1987; 43: 2609
• 5 Johnson AW. Ylide Chemistry. Academic Press; New York: 1966
• 6a Li A.-H, Dai L.-X, Aggarwal VK. Chem. Rev. 1997; 97: 2341
• 6b Vedejs E. Acc. Chem. Res. 1984; 17: 358
• 6c Ye T, McKervey MA. Chem. Rev. 1994; 94: 1091
• 7a Traynelis VJ, McSweeney SJ. V. J. Org. Chem. 1966; 31: 243
• 7b Pagni RM, Watson CR. J. Chem. Soc., Chem. Commun. 1974; 224
• 8a Dean FM. Naturally Occurring Oxygen Ring Compounds. Butterworth; London: 1963
• 8b Harborne JB. The Flavonoids. Chapman and Hall; London: 1994
• 8c Chang LC, Kinghorn AD. Bioactive Compounds from Natural Sources: Isolation, Characterization and Biological Properties. Taylor and Francis; London: 2001
• 8d Cao S, Schilling JK, Miller JS, Andriantsiferana R, Rasamison VE, Kingston DG. I. J. Nat. Prod. 2004; 67: 454
• 8e Harborne JB, Williams CA. Nat. Prod. Rep. 2001; 18: 310
• 9 Fridén-Saxin M, Pemberton N, da Silva Andersson K, Dyrager C, Friberg A, Grøtli M, Luthman K. J. Org. Chem. 2009; 74: 2755
• 10a Kabbe H.-J, Widdig A. Angew. Chem., Int. Ed. Engl. 1982; 21: 247
• 10b Cox B, Waigh RD. Synthesis 1989; 709
• 10c Tímár T, Eszenyi T, Sebők P, Lévai A. J. Heterocycl. Chem. 2000; 37: 1389
• 11a Patonay T, Varma RS, Vass A, Lévai A, Dudás J. Tetrahedron Lett. 2001; 42: 1403
• 11b Bianco A, Cavarischia C, Farina A, Guiso M, Marra C. Tetrahedron Lett. 2003; 44: 9107
• 11c Bianco A, Cavarischia C, Guiso M. Eur. J. Org. Chem. 2004; 2894
• 11d Biddle MM, Lin M, Scheidt KA. J. Am. Chem. Soc. 2007; 129: 3830
• 11e Wallén EA. A, Dahlén K, Grøtli M, Luthman K. Org. Lett. 2007; 9: 389
• 11f Park JY, Ullapu PR, Choo H, Lee JK, Min S.-J, Pae AN, Kim Y, Baek D.-J, Cho YS. Eur. J. Org. Chem. 2008; 5461
• 11g Cui H, Li P, Chai Z, Zheng C, Zhao G, Zhu S. J. Org. Chem. 2009; 74: 1400
• 12a Iwasaki H, Kume T, Yamamoto Y, Akiba K.-y. Tetrahedron Lett. 1987; 28: 6355
• 12b Kelly SE, Vandeplas BC. J. Org. Chem. 1991; 56: 1325
• 12c Coutts SJ, Wallace TW. Tetrahedron 1994; 50: 11755
• 12d Meng L.-G, Liu H.-F, Wei J.-L, Gong S.-N, Xue S. Tetrahedron Lett. 2010; 51: 1748
• 12e Patil SG, Bagul RR, Swami MS, Hallale SN, Kamble VM. J. Chem. Pharm. Res. 2011; 3: 457
• 13a Cohen N, Weber G, Banner BL, Lopresti RJ, Schaer B, Focella A, Zenchoff GB, Chiu AM, Todaro L. J. Med. Chem. 1989; 32: 1842
• 13b Koyama H, Miller DJ, Boueres JK, Desai RC, Jones AB, Berger JP, MacNaul KL, Kelly LJ, Doebber TW, Wu MS, Zhou G, Wang P.-R, Ippolito MC, Chao Y.-S, Agrawal AK, Franklin R, Heck JV, Wright SD, Moller DE, Sahoo SP. J. Med. Chem. 2004; 47: 3255
• 14a Witiak DT, Stratford ES, Nazareth R, Wagner G, Feller DR. J. Med. Chem. 1971; 14: 758
• 14b Clarke PD, Fitton AO, Suschitzky H, Wallace TW, Dowlatshahi HA, Suschitzky JL. Tetrahedron Lett. 1986; 27: 91
• 14c Sarges R, Hank RF, Blake JF, Bordner J, Bussolotti DL, Hargrove DM, Treadway JL, Gibbs EM. J. Med. Chem. 1996; 39: 4783
• 15 Annoura H, Fukunaga A, Uesugi M, Tatsuoka T, Horikawa Y. Bioorg. Med. Chem. Lett. 1996; 6: 763
• 16 Aggarwal VK, Harvey JN, Robiette R. Angew. Chem. Int. Ed. 2005; 44: 5468
• 17 Yamauchi K, Nakamura K, Kinoshita M. J. Org. Chem. 1978; 43: 1593
• 18 Aggarwal VK, Grange E. Chem. Eur. J. 2006; 12: 568
• 19 Mahapatra T, Jana N, Nanda S. Tetrahedron: Asymmetry 2008; 19: 1224
• 20 Aggarwal VK, Harvey JN, Richardson J. J. Am. Chem. Soc. 2002; 124: 5747
• 21a Cances E, Mennucci B, Tomasi J. J. Chem. Phys. 1997; 107: 3032
• 21b Mennucci B, Tomasi J. J. Chem. Phys. 1997; 106: 5151
• 21c Barone V, Cossi M, Tomasi J. J. Chem. Phys. 1997; 107: 3210
• 21d Barone V, Cossi M, Tomasi J. J. Comput. Chem. 1998; 19: 404
• 21e Tomasi J, Mennucci B, Cancès E. J. Mol. Struct.: THEOCHEM 1999; 464: 211
• 22 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Foresman JB, Ortiz JV, Cioslowski J, Fox DJ. Gaussian 09, Revision B.01. Gaussian; Wallingford CT: 2010
• 23a Gonzalez C, Schlegel HB. J. Phys. Chem. 1990; 94: 5523
• 23b Gonzalez C, Schlegel HB. J. Phys. Chem. 1991; 95: 5853