The Journal of Organic Chemistry
Article
0.866 mmol) was then added through the ground glass joint, the
septum was replaced, and the resulting bright red solution was stirred
under static nitrogen for 3 h. The solvent was removed slowly in
vacuo. An oven-dried vacuum adapter was attatched. Chlorobenzene
(ratio 1.000, volume 1.5 mL) was then added through the reflux
condenser, followed by freshly distilled triethoxymethane (0.917 mL,
5.51 mmol), and the resulting solution was refluxed under nitrogen at
110 °C for 16 h. Purification by a 25 g Biotage column (50% EtOAc/
hex, Rf1= 0.4) gave azolium salt R as a tan powder (215 mg, 63%
yield). H NMR (500 MHz, CDCl3): δ 10.23 (s, 1H), 7.25 (s, 1H),
7.21−7.12 (m, 2H), 6.99 (s, 2H), 6.02 (d, J = 3.9 Hz, 1H), 5.02 (dd, J
= 4.2, 1.5 Hz, 3H), 3.14−3.07 (m, 2H), 2.36 (d, J = 16.7 Hz, 6H), 2.04
(s, 6H), 1.63 (s, 1H). 13C NMR (126 MHz, CDCl3): δ 150.1, 143.5,
141.9, 138.3, 137.0, 135.5, 131.2, 130.6, 129.9, 125.4, 124.4, 77.8, 62.2,
60.4, 37.1, 21.4, 21.3, 17.2. LRMS (ESI): mass calcd for C22H24N3O
[M − BF4]+, 346; found, 346.
(18) Wang, M. H.; Cohen, D. T.; Schwamb, C. B.; Mishra, R. K.;
Scheidt, K. A. J. Am. Chem. Soc. 2015, 137, 5891.
(19) Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A.,
Yamamoto, H., Eds.; Springer: New York, 1999.
(20) C-H Activation; Yu, J.-Q., Shi, Z., Eds.; Springer Berlin
Heidelberg: Berlin, 2010; Vol. 292.
(21) Cho, B. T. Tetrahedron 2006, 62, 7621.
(22) Cho, B. T. Chem. Soc. Rev. 2009, 38, 443.
(23) Gladiali, S.; Alberico, E. Chem. Soc. Rev. 2006, 35, 226.
(24) Magano, J.; Dunetz, J. R. Org. Process Res. Dev. 2012, 16, 1156.
(25) Mohr, J. T.; Hong, A. Y.; Stoltz, B. M. Nat. Chem. 2009, 1, 359.
(26) Rueping, M.; Kuenkel, A.; Atodiresei, I. Chem. Soc. Rev. 2011,
40, 4539.
(27) Miyamoto, K.; Ohta, H. J. Am. Chem. Soc. 1990, 112, 4077.
(28) Matsumoto, K.; Tsutsumi, S.; Ihori, T.; Ohta, H. J. Am. Chem.
Soc. 1990, 112, 9614.
(29) Matoishi, K.; Ueda, M.; Miyamoto, K.; Ohta, H. J. Mol. Catal. B:
Enzym. 2004, 27, 161.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
(30) Oudeyer, S.; Brier
2014, 6103.
̀
e, J.-F.; Levacher, V. Eur. J. Org. Chem. 2014,
S
(31) Pracejus, H. Justus Liebigs Ann. Chem. 1960, 634, 9.
(32) Duhamel, L.; Plaquevent, J. C. J. Am. Chem. Soc. 1978, 100,
7415.
(33) Vedejs, E.; Kruger, A. W.; Lee, N.; Sakata, S. T.; Stec, M.; Suna,
E. J. Am. Chem. Soc. 2000, 122, 4602.
Experimental procedures, spectral data, and crystallo-
X-ray data for compound C19H19BrO4 (CIF)
(34) Fehr, C. Angew. Chem., Int. Ed. 2007, 46, 7119.
(35) Poisson, T.; Dalla, V.; Marsais, F.; Dupas, G.; Oudeyer, S.;
Levacher, V. Angew. Chem., Int. Ed. 2007, 46, 7090.
(36) Cheon, C. H.; Yamamoto, H. J. Am. Chem. Soc. 2008, 130, 9246.
(37) Brunner, H.; Baur, Markus A. Eur. J. Org. Chem. 2003, 2003,
2854.
(38) Amere, M.; Lasne, M.-C.; Rouden, J. Org. Lett. 2007, 9, 2621.
(39) Marinescu, S. C.; Nishimata, T.; Mohr, J. T.; Stoltz, B. M. Org.
Lett. 2008, 10, 1039.
AUTHOR INFORMATION
Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
■
(40) Hodous, B. L.; Ruble, J. C.; Fu, G. C. J. Am. Chem. Soc. 1999,
121, 2637.
(41) Navarre, L.; Martinez, R.; Genet, J.-P.; Darses, S. J. Am. Chem.
Soc. 2008, 130, 6159.
(42) Nishimura, T.; Hirabayashi, S.; Yasuhara, Y.; Hayashi, T. J. Am.
ACKNOWLEDGMENTS
Financial support was provided by the NIH NIGMS
(GM073072).
■
Chem. Soc. 2006, 128, 2556.
(43) Reynolds, N. T.; Rovis, T. J. Am. Chem. Soc. 2005, 127, 16406.
(44) Vora, H. U.; Rovis, T. J. Am. Chem. Soc. 2010, 132, 2860.
(45) Jousseaume, T.; Wurz, N. E.; Glorius, F. Angew. Chem., Int. Ed.
2011, 50, 1410.
(46) Wang, X.-N.; Lv, H.; Huang, X.-L.; Ye, S. Org. Biomol. Chem.
2009, 7, 346.
REFERENCES
■
(1) Bugaut, X.; Glorius, F. Chem. Soc. Rev. 2012, 41, 3511.
(2) Izquierdo, J.; Hutson, G. E.; Cohen, D. T.; Scheidt, K. A. Angew.
Chem., Int. Ed. 2012, 51, 11686.
(3) Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F. Nature
2014, 510, 485.
(47) Concellon
351, 3001.
́
, C.; Duguet, N.; Smith, A. D. Adv. Synth. Catal. 2009,
(4) Flanigan, D. M.; Romanov-Michailidis, F.; White, N. A.; Rovis, T.
(48) Chen, X.; Fong, J. Z. M.; Xu, J.; Mou, C.; Lu, Y.; Yang, S.; Song,
B.-A.; Chi, Y. R. J. Am. Chem. Soc. 2016, 138, 7212.
(49) Mattson, A. E.; Bharadwaj, A. R.; Scheidt, K. A. J. Am. Chem. Soc.
2004, 126, 2314.
(50) Mattson, A. E.; Scheidt, K. A. Org. Lett. 2004, 6, 4363.
(51) Mattson, A. E.; Zuhl, A. M.; Reynolds, T. E.; Scheidt, K. A. J.
Am. Chem. Soc. 2006, 128, 4932.
(52) Mattson, A. E.; Bharadwaj, A. R.; Zuhl, A. M.; Scheidt, K. A. J.
Org. Chem. 2006, 71, 5715.
(53) Mattson, A. E.; Scheidt, K. A. J. Am. Chem. Soc. 2007, 129, 4508.
(54) Suzuki, Y.; Yamauchi, K.; Muramatsu, K.; Sato, M. Chem.
Commun. 2004, 2770.
Chem. Rev. 2015, 115, 9307.
(5) Mahatthananchai, J.; Bode, J. W. Acc. Chem. Res. 2014, 47, 696.
(6) Yetra, S. R.; Patra, A.; Biju, A. T. Synthesis 2015, 47, 1357.
(7) Menon, R. S.; Biju, A. T.; Nair, V. Chem. Soc. Rev. 2015, 44, 5040.
(8) Menon, R. S.; Biju, A. T.; Nair, V. Beilstein J. Org. Chem. 2016, 12,
444.
(9) Chan, A.; Scheidt, K. A. Org. Lett. 2005, 7, 905.
(10) Maki, B. E.; Chan, A.; Scheidt, K. A. Synthesis 2008, 2008, 1306.
(11) Maki, B. E.; Patterson, E. V.; Cramer, C. J.; Scheidt, K. A. Org.
Lett. 2009, 11, 3942.
(12) Lee, J. M.; Na, Y.; Han, H.; Chang, S. Chem. Soc. Rev. 2004, 33,
302.
(55) Kano, T.; Sasaki, K.; Maruoka, K. Org. Lett. 2005, 7, 1347.
(56) De Sarkar, S.; Biswas, A.; Song, C. H.; Studer, A. Synthesis 2011,
2011, 1974.
(13) Berkessel, A.; Groger, H. Asymmetric Organocatalysis: From
Biomimetic Concepts to Applications in Asymmetric Synthesis; Blackwell
Science Publishers: Oxford, 2005.
(57) Kuwano, S.; Harada, S.; Kang, B.; Oriez, R.; Yamaoka, Y.;
Takasu, K.; Yamada, K.-i. J. Am. Chem. Soc. 2013, 135, 11485.
(58) Lu, S.; Poh, S. B.; Siau, W.-Y.; Zhao, Y. Angew. Chem., Int. Ed.
2013, 52, 1731.
(14) Allen, A. E.; MacMillan, D. W. C. Chem. Sci. 2012, 3, 633.
(15) Cohen, D. T.; Scheidt, K. A. Chem. Sci. 2012, 3, 53.
(16) Inamdar, S. M.; Shinde, V. S.; Patil, N. T. Org. Biomol. Chem.
2015, 13, 8116.
(59) De Sarkar, S.; Biswas, A.; Samanta, R. C.; Studer, A. Chem. - Eur.
(17) Wang, M. H.; Scheidt, K. A. Angew. Chem., Int. Ed. 2016, 55,
14912.
J. 2013, 19, 4664.
M
J. Org. Chem. XXXX, XXX, XXX−XXX