A New Route to N¹-Substituted Uracil Derivatives Using Hypervalent Iodine

Abstract

In continuation of our previous study, oxidative coupling reactions of uracil with allylsilane or enol ethers were examined using diacetoxyiodobenzene. The reaction of persilylated uracil with 3,4-dihydro-2H-pyran in the presence of TMSOTf and PhI(OAc)₂ resulted in the formation of a dihydropyranyluracil derivative, although the yield was low. In an extension of the oxidative coupling reaction, a novel glycosylation reaction using glycal derivatives as substrates was also developed. The treatment of persilylated uracil and 3,4-dihydro-2H-pyran with (PhSe)₂ and PhI(OAc)₂ in the presence of a catalytic amount of TMSOTf gave a 2,3-anti-derivative of 1-(3-phenylselanyltetrahydropyran-2-yl)uracil stereoselectively and in good yield.

Key words

hypervalent iodine - nucleoside - oxidative coupling - glycosylation - glycal

• References


Recent reports:
• 1a Fan X, Wang Y, Qu Y, Xu H, He Y, Zhang X, Wang J. J. Org. Chem. 2011; 76: 982
• 1b Peacock H, Maydanovych O, Beal PA. Org. Lett. 2010; 12: 1044
• 1c Plant A, Thompson P, William DM. J. Org. Chem. 2009; 74: 4870
• 1d Smith DB, Kalayanov G, Sund C, Winqvist A, Pinho P, Maltseva T, Morisson V, Leveque V, Rajyaguru S, Le PogamS, Najera I, Benkestock K, Zhou X.-X, Maag H, Cammack N, Martin JA, Swallow S, Johansson NJ, Klumpp K, Smith M. J. Med. Chem. 2009; 52: 219
• 1e Spitale RC, Heller MG, Pelly AJ, Wedekind JE. J. Org. Chem. 2007; 72: 8551

Recent reports:
• 2a Dalençon S, Youcef RA, Pipelier M, Maisonneuve V, Dubreuil D, Huet F, Legoupy S. J. Org. Chem. 2011; 76: 8059
• 2b Saneyoshi H, Deschamps JR, Marquez VE. J. Org. Chem. 2010; 75: 7659
• 2c Jiang MX.-W, Jin B, Gage JL, Priour A, Savela G, Miller MJ. J. Org. Chem. 2006; 71: 4164

Recent reports:
• 3a Huang Q, Herdewijin P. J. Org. Chem. 2011; 76: 3742
• 3b Reddy PG, Chun B.-W, Zhang H.-R, Rachakonda S, Ross BS, Sofia MJ. J. Org. Chem. 2011; 76: 3782
• 3c Seth PP, Vasquez G, Allerson CA, Berdeja A, Gaus H, Kinberger GA, Prakash TP, Migawa MT, Bhat B, Swayze EE. J. Org. Chem. 2010; 75: 1569
• 3d Prévost M, St-Jean O, Guindon Y. J. Am. Chem. Soc. 2010; 132: 12433
• 3e Stauffer CS, Datta A. J. Org. Chem. 2008; 73: 4166
• 3f Sabatino D, Damha MJ. J. Am. Chem. Soc. 2007; 129: 8259
• 3g Jean-Baptiste L, Yemets S, Legay R, Lequeux T. J. Org. Chem. 2006; 71: 2352
• 3h Neogi A, Majhi TP, Mukhopadhyay R, Chattopadyay P. J. Org. Chem. 2006; 71: 3291
• 3i Gagneron J, Gosselin G, Mathé C. J. Org. Chem. 2005; 70: 6891
• 4a Yoshimura Y, Yamazaki Y, Saito Y, Natori Y, Imamichi T, Takahata H. Bioorg. Med. Chem. Lett. 2011; 21: 3313
• 4b Yoshimura Y, Yamazaki Y, Saito Y, Takahata H. Tetrahedron 2009; 65: 9091
• 4c Yoshimura Y, Yamazaki Y, Kawahata M, Yamaguchi K, Takahata H. Tetrahedron Lett. 2007; 48: 4519
• 4d Yoshimura Y, Kuze T, Ueno M, Komiya F, Haraguchi K, Tanaka H, Kano F, Yamada K, Asami K, Kaneko N, Takahata H. Tetrahedron Lett. 2006; 47: 591
• 4e Yoshimura Y, Kitano K, Yamada K, Satoh H, Watanabe M, Miura S, Sakata S, Sasaki T, Matsuda A. J. Org. Chem. 1997; 62: 3140
• 4f Yoshimura Y, Kitano K, Satoh H, Watanabe M, Miura S, Sakata S, Sasaki T, Matsuda A. J. Org. Chem. 1996; 61: 822
• 5a Yoshimura Y, Asami K, Imamichi T, Kuroda T, Shiraki K, Tanaka H, Takahata H. J. Org. Chem. 2010; 75: 4161
• 5b Yoshimura Y, Asami K, Matsui H, Tanaka H, Takahata H. Org. Lett. 2006; 8: 6015
• 6 Yoshimura Y, Ohta M, Imahori T, Imamichi T, Takahata H. Org. Lett. 2008; 10: 3449
• 7 During the course of our investigation, the intramolecular oxidative C–N bond forming reaction using Cu(OTf)₂ and PhI(OAc)₂ has been reported: Cho SH, Yoon J, Chang S. J. Am. Chem. Soc. 2011; 133: 5996
• 8 The H-H COSY spectrum of 10d and 10e showed that there is no cross peak corresponding to the correlation between H1′ and H2′ of 10e. This revealed that a dihedral angle of H1′-C1′-C2′-H2′ should be around 90°. From this result, 10e was determined to be a 1′,2′-trans-isomer
• 9 The C2-acylglycosylation of glycals with PhI(OCOR)₂ in the presence of Et₂O·BF₃ was reported to proceed via a C2-phenyliodonium (I^III) intermediate: Shi L, Kim Y.-J, Gin DY. J. Am. Chem. Soc. 2001; 123: 6939
• 10 Singh FV, Wirth T. Org. Lett. 2011; 13: 6504

In contrast, the reaction of glycal derivatives with (PhSe)₂, PhI(OAc)₂, and NaN₃ gave 2-azido-1-phenylseleno-glycoside selectively:
• 11a Litjens RE. J. N, den Heeten R, Timmer MS. M, Overkleeft HS, van der Marel GA. Chem.–Eur. J. 2005; 11: 1010
• 11b Jiaang W.-T, Chang M.-Y, Tseng P.-H, Chen S.-T. Tetrahedron Lett. 2000; 41: 3127
• 11c Santoyo-Gonzalez F, Calvo-Flores FG, García-Mendoza P, Hernández-Mateo F, Isac-García J, Robles-Díaz R. J. Org. Chem. 1993; 58: 6122

For example, see:
• 12a De Clercq E. Biochem. Pharmacol. 2011; 82: 99
• 12b Esté JA, Cihlar T. Antiviral Res. 2010; 85: 25
• 12c Meadows DC, Gervey-Hague J. ChemMedChem 2006; 1: 16
• 12d Imamichi T. Curr. Pharm. Design 2004; 10: 4039
• 13 Imanieh H, Quayle P, Voaden M, Conway J. Tetrahedron Lett. 1992; 33: 543
• 14 The stereochemistries of 15d,e were determined by NOE experiments: 15d showed a NOE (3.1%) between H-6 of the uracil ring and one of the methylene protons on the siloxymethyl group on C6 of tetrahydropyran. On the other hand, in the case of 15e, NOEs (9.9% and 2.3%) were found between the H-2 of tetrahydropyran (anomeric proton) and the methylene protons of the siloxymethyl group. The stereochemistries of 15f,g were estimated by comparison with the ¹H NMR spectra of 15d,e
• 15a Díaz Y, El-Laghdach A, Matheu MI, Castillón S. J. Org. Chem. 1997; 62: 1501
• 15b Wilson L, Lotta D. Tetrahedron Lett. 1990; 31: 1815