Job/Unit: O42673
/KAP1
Date: 15-09-14 17:51:37
Pages: 11
DMAP-Catalysed Sulfinylation of Diacetone Glucose
(R)-N-Benzyl-tert-butanesulfinamide (20RS):[7] Reaction time
45 min. Purified by flash chromatography (EtOAc/hexane, 1:1, to
EtOAc) to give 20RS (211 mg, 1 mmol, 62%) as a white solid, m.p.
64–65 °C. [α]2D0 = –31 (c = 1.0, CHCl3). 1H NMR (500 MHz,
CDCl3): δ = 7.38–7.30 (m, 5 H), 4.39 (dd, J = 13.7, J = 4.7 Hz, 1
H), 4.29 (dd, J = 13.7, J = 4.7 Hz, 1 H), 1.29 (s, 9 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 138.53, 128.64, 128.12, 127.71,
55.95, 49.46, 22.69 ppm. HRMS: calcd. for C11H17NOS [M + H]+
212.1110; found 212.1109. The ee was determined by HPLC [Chi-
ralcel® AD (iPrOH/hexane, 2:98; 1 mL/min)]: tR = 19.8 min (R iso-
mer) and 24.1 min (S isomer).
M. T. Withnall, J.-C. Aloup, I. Cavero, D. Fargen, C. James, S.
Mondot, J. Med. Chem. 1992, 35, 3613; b) N. Khiar, S. Werner,
S. Mallouk, F. Lieder, A. Alcudia, I. Fernandez, J. Org. Chem.
2009, 74, 6002.
a) M. C. Carreño, Chem. Rev. 1995, 95, 1717; b) M. C. Car-
reno, G. Hernandez-Torres, M. Ribagorda, A. Urbano, Chem.
Commun. 2009, 6129; c) H. Pellissier, Tetrahedron 2006, 62,
5559.
[7]
[8]
a) S. Kobayashi, C. Ogawa, H. Konishi, M. Sugiura, J. Am.
Chem. Soc. 2003, 125, 6610; b) A. Massa, A. V. Malkov, P.
Kocovky, A. Scettri, Tetrahedron Lett. 2003, 44, 7179; c) G.
Rowlands, W. K. Barnes, Chem. Commun. 2003, 2712; d) I.
Fernández, V. Valdivia, B. Gori, F. Alcudia, E. Álvarez, N.
Khiar, Org. Lett. 2005, 7, 1307; e) I. Fernández, V. Valdivia,
M. Pernía Leal, N. Khiar, Org. Lett. 2007, 9, 2215; f) I.
Fernández, A. Alcudia, B. Gori, V. Valdivia, R. Recio, M. V.
García, N. Khiar, Org. Biomol. Chem. 2010, 8, 4388.
a) I. Fernández, N. Khiar, in: Organosulfur Chemistry in Asym-
metric Synthesis (Eds.: T. Toru, C. Bolm), Wiley-VCH,
Weinheim, Germany, 2008, p. 265; b) R. Mariz, X. Luan, M.
Gatti, A. Linden, R. Dorta, J. Am. Chem. Soc. 2008, 130, 2172;
c) J. Bürgi, R. Mariz, M. Gatti, E. Drinkel, X. Luan, S. Blu-
mentritt, A. Linden, R. Dorta, Angew. Chem. Int. Ed. 2009,
48, 2768; Angew. Chem. 2009, 121, 2806; d) T. Thaler, L.-N.
Guo, A. K. Steib, A. K. M. Raducan, K. Karaghiosoff, P.
Mayer, P. Knochel, Org. Lett. 2011, 13, 3182; e) X. Feng, Y.
Wang, B. Wei, J. Yang, H. Du, Org. Lett. 2011, 13, 3300; f) G.
Chen, J. Gui, L. Li, L. Liao, Angew. Chem. Int. Ed. 2011, 50,
7681; Angew. Chem. 2011, 123, 7823; g) X. Feng, B. Wei, J.
Yang, H. Du, Org. Biomol. Chem. 2011, 9, 5927; h) F. Xue, X.
Li, B. Wan, J. Org. Chem. 2011, 76, 7256; i) Y. Wang, X. Feng,
H. Du, Org. Lett. 2011, 13, 4954; j) N. Khiar, V. E. Valdívia,
A. Salvador, A. Chelouan, A. Alcudia, I. Fernández, Adv.
Synth. Catal. 2013, 355, 1303; k) V. E. Valdivia, I. Fernández,
N. Khiar, Org. Biomol. Chem. 2014, 12, 1211.
a) C. Mioskowski, G. Solladié, Tetrahedron 1980, 36, 227; b)
G. Solladié, J. Hutt, A. Girardin, Synthesis 1987, 173.
K. K. Andersen, Tetrahedron Lett. 1962, 3, 93.
M. Casey, A. C. Manage, L. Nezhat, Tetrahedron Lett. 1988,
29, 5821.
a) G. Liu, D. A. Cogan, T. D. Owens, T. P. Tang, J. A. Ellman,
J. Org. Chem. 1999, 64, 1278; b) T. D. Owens, F. J. Hollander,
A. G. Oliver, J. A. Ellman, J. Am. Chem. Soc. 2001, 123, 1539.
J. L. García-Ruano, I. Fernández, M. del Prado, A. Alcudia,
Tetrahedron: Asymmetry 1996, 7, 3407.
J. Adrio, J. C. Carretero, J. Am. Chem. Soc. 1999, 121, 7441.
T. D. Owens, F. J. Hollander, A. J. Oliver, J. A. Ellman, J. Am.
Chem. Soc. 2001, 123, 1539.
(R)-N-tert-Butyl-tert-butanesulfinamide (21RS): Reaction time
45 min. Purified by flash chromatography (EtOAc/hexane, 1:1, to
EtOAc) to give 21RS (145 mg, 0.82 mmol, 50%) as a white solid,
1
m.p. 79–81 °C. [α]2D0 = –38 (c = 2.0, CHCl3). H NMR (500 MHz,
CDCl3): δ = 3.01 (br. s, 1 H), 1.31 (s, 9 H), 1.20 (s, 9 H) ppm. 13C
NMR (125 MHz, CDCl3): δ = 55.1, 53.1, 31.0, 22.4 ppm. HRMS:
calcd. for C8H20NOS [M + H]+ 178.1266; found 178.1265.
[9]
(R)-N-Allyl-tert-butanesulfinamide (22RS): Reaction time 2 h. Puri-
fied by flash chromatography (hexane/EtOAc, 1:1) to give 22RS
(219 mg, 1.36 mmol, 83%) as a yellow oil. [α]2D0 = +12.3 (c = 0.6,
CHCl3). 1H NMR (500 MHz, CDCl3): δ = 5.95–5.86 (m, 1 H), 5.26
(d, J = 17.1 Hz, 1 H), 5.16 (d, J = 10.2 Hz, 1 H), 3.74–3.65 (m, 1
H), 3.47–3.39 (m, 1 H), 1.22 (s, 9 H) ppm. 13C NMR (125 MHz,
CDCl3): δ = 135.2, 117.0, 55.7, 48.1, 22.5 ppm. C7H15NOS
(161.27): C 52.13, H 9.38, N 8.69, S 19.88; found C 52.36, H 9.26,
N 8.39, S 20.10. The ee was determined by HPLC [Chiralcel® AS-
H (n-hexane/2-propanol, 90:10; 0.7 mL/min)]: tR = 13.8 min (S-iso-
mer), 24.7 min (R-isomer).
Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures for the synthesis of compounds 9RS,
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9SS, 9RS, and 9SS. Copies of H and 13C NMR spectra.
[11]
[12]
Acknowledgments
[13]
[14]
This work was supported by the Ministerio de Economía y Compe-
titividad (MEC) (grant numbers CTQ2010-21755-CO2-02 and
CTQ2013-49066-C2-2-R) and the Junta de Andalucía (grant
number P11-FQM-8046). A. C. thanks the Ministerio de Asuntos
Exteriores y de Cooperacion for a predoctoral MAEC-AECID
grant. CITIUS is gratefully thanked for the NMR facilities.
[15]
[16]
[17]
[18]
[19]
M. Obringer, F. Colobert, B. Neugnot, G. Solladié, Org. Lett.
2003, 5, 629.
F. Colobert, V. E. Vadivia, S. Choppin, F. Leroux, I.
Fernández, N. Khiar, Org. Lett. 2009, 11, 5130.
a) N. Khiar, A. Salvador, A. Chelouan, A. Alcudia, I.
Fernández, Org. Biomol. Chem. 2012, 10, 2366; b) N. Khiar, A.
Salvador, V. E. Valdívia, A. Chelouan, A. Alcudia, E. Álvarez,
I. Fernández, J. Org. Chem. 2013, 78, 6510.
a) J. Legros, J. R. Dehli, C. Bolm, Adv. Synth. Catal. 2005, 347,
19; b) G. E. O’Mahony, A. Ford, A. R. Maguire, J. Sulfur
Chem. 2013, 34, 301.
F. Rebiere, O. Samuel, L. Ricard, H. B. Kagan, J. Org. Chem.
1991, 56, 5991.
J. L. García Ruano, C. Alemparte, M. T. Aranda, M. M. Zar-
zuelo, Org. Lett. 2003, 5, 75.
Z. Han, D. Krishnamurthy, P. Grover, Q. K. Fang, C. Sen-
anayake, J. Am. Chem. Soc. 2002, 124, 7880.
[1] a) I. Fernández, N. Khiar, Chem. Rev. 2003, 103, 3651; b) E.
Wojaczynska, J. Wojaczynski, Chem. Rev. 2010, 110, 4303; c) C.
Senanayake, D. Krishnamurthy, Z.-H. Lu, Z. Han, I. Gallou,
Aldrichim. Acta 2005, 38, 93.
[2] R. Bentley, Chem. Soc. Rev. 2005, 34, 609.
[3] a) I. Agranat, H. Caner, J. Caldwell, Nat. Rev. Drug Discovery
2002, 1, 753; b) E. Carlsson, P. Lindberg, S. von Unge, Chem.
Brit. 2002, 38, 42; c) T. M. Khomenko, K. P. Volcho, N. I. Ko-
marova, N. F. Salakhutdinov, Russ. J. Org. Chem. 2008, 44,
124; d) B. Jiang, X.-L. Zhao, J.-J. Dong, W.-J. Wang, Eur. J.
Org. Chem. 2009, 987.
[4] a) J. Ternois, F. Guillen, J.-C. Plaquevent, G. Coquerel, Tetra-
hedron: Asymmetry 2007, 18, 2959; b) J. Cao, T. E. Prisinzano,
O. M. Okunola, T. Kopajtic, M. Shook, J. L. Katz, A. M. New-
man, ACS Med. Chem. Lett. 2011, 2, 48.
[5] a) R. Maguire, S. Papot, A. Ford, S. Touhey, R. O’Connor,
M. Clynes, Synlett 2001, 41; b) F. Naso, C. Cardellicchio, F.
Affortunato, M. A. M. Capozzi, Tetrahedron: Asymmetry 2006,
17, 3226.
[6] a) T. J. Brown, R. F. Chapman, D. C. Cook, T. W. Hart, I. M.
McLay, R. Jordan, J. S. Mason, M. N. Palfreyman, R. J. Walsh,
[20]
[21]
[22]
[23]
[24]
[25]
M. A. M. Capozzi, C. Cardellicchio, F. Naso, Eur. J. Org.
Chem. 2004, 1855.
a) D. R. Dragoli, M. T. Burdett, J. A. Ellman, J. Am. Chem.
Soc. 2001, 123, 10127; b) D. J. Weix, J. A. Ellman, Org. Lett.
2003, 5, 1317.
Eur. J. Org. Chem. 0000, 0–0
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