G
L. Yang, Q. Zeng
Paper
Synthesis
4,4-Dimethyl-1,1-diphenylpent-1-en-3-one (2w)22
Department of Science and Technology of Sichuan Province
(2016HH0074)
Colorless oil; yield: 65 mg (82%).
Education Department of Sichuan Province (16ZA0084)
Chengdu Science and Technology Bureau (2015-HM01-00362-SF)
State Key Laboratory of Geohazard Prevention and Geoenvironment
Protection Independent Research Project (SKLGP2016Z004)
1H NMR (CDCl3, 400 MHz): δ = 7.38 (dd, J = 3.9, 2.6 Hz, 5 H), 7.36 (d, J
= 2.0 Hz, 1 H), 7.34–7.32 (m, 1 H), 7.32–7.30 (m, 1 H), 7.20–7.16 (m, 2
H), 6.94 (s, 1 H), 1.24 (s, 9 H).
13C NMR (CDCl3, 101 MHz): δ = 205.46, 154.60, 141.81, 139.45,
129.21, 129.07, 128.40, 128.38, 128.00, 121.59, 44.14, 26.63.
HRMS (ESI): m/z [M + Na]+ calcd for C19H20ONa+: 287.1406; found:
Supporting Information
287.1405.
Supporting information for this article is available online at
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3-Phenyl-3-(trimethylsilyl)-2,3-dihydroinden-1-one (2x)23
Orange oil; yield: 30 mg (36%).
1H NMR (CDCl3, 400 MHz): δ = 7.86–7.82 (m, 1 H), 7.73–7.67 (m, 2 H),
7.42 (m, 1 H), 7.39–7.35 (m, 2 H), 7.35–7.30 (m, 2 H), 7.23–7.18 (m, 1
H), 3.28 (d, J = 19.6 Hz, 1 H), 3.03 (d, J = 19.6 Hz, 1 H), –0.01 (s, 9 H).
13C NMR (CDCl3, 101 MHz): δ = 205.65, 159.11, 144.54, 136.61,
134.30, 128.44, 127.71, 126.87, 126.71, 125.58, 124.20, 49.83, 42.99, –
2.74.
References
(1) (a) The Chemistry of Enones; Patai, S.; Rappoport, Z., Eds.; Wiley:
New York, 1989. (b) Comprehensive Organic Synthesis;
V
o
l
Trost, B.
M.; Fleming, I.; Semmelhack, M., Eds.; Pergamon: Oxford, 1991,
4. (c) Otera, J. Modern Carbonyl Chemistry; Wiley-VCH: Wein-
heim, 2000.
HRMS (ESI): m/z [M + Na]+ calcd for C18H20OSiNa+: 303.1176; found:
303.1177.
(2) (a) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863.
(b) Choudary, B. M.; Kantam, M. L.; Ranganath, K. V. S.;
Mahendar, K.; Sreedhar, B. J. Am. Chem. Soc. 2004, 126, 3396.
(c) Kurti, L.; Czakó, B. Strategic Applications of Named Reactions
in Organic Synthesis; Elsevier: Amsterdam, 2005. (d) Meinwald,
J. J. Chem. Educ. 1965, 42, A910.
2-Methylene-1,5-diphenylpentane-1,5-dione (2y)24
Colorless oil; yield: 41 mg (52%).
1H NMR (CDCl3, 400 MHz): δ = 8.01 (d, J = 7.6 Hz, 2 H), 7.76 (d, J = 7.6
Hz, 2 H), 7.57 (s, 2 H), 7.47 (d, J = 9.8 Hz, 4 H), 5.99 (s, 1 H), 5.71 (s, 1
H), 3.27 (t, J = 7.3 Hz, 2 H), 2.95 (t, J = 7.3 Hz, 2 H).
(3) Meyer, K. H.; Schuster, K. Ber. Dtsch. Chem. Ges. 1922, 55, 819.
(4) Trost, B. M. Science 1991, 254, 1471.
(5) (a) Swaminathan, S.; Narayanan, K. V. Chem. Rev. 1971, 71, 429.
(b) Rupe, H.; Kambli, E. Helv. Chim. Acta 1926, 9, 672.
(6) (a) Okamoto, N.; Sueda, T.; Yanada, R. J. Org. Chem. 2014, 79,
9854. (b) Nikolaev, A.; Orellana, A. Org. Lett. 2015, 17, 5796.
(c) Xiong, Y. P.; Wu, M. Y.; Zhang, X. Y.; Ma, C. L.; Huang, L.;
Zhao, L. J.; Tan, B.; Liu, X. Y. Org. Lett. 2014, 16, 1000. (d) Yu, Y.;
Yang, W. B.; Pflasterer, D.; Hashmi, A. S. K. Angew. Chem. Int. Ed.
2014, 53, 1144. (e) Collins, B. S. L.; Suero, M. G.; Gaunt, M. J.
Angew. Chem. Int. Ed. 2013, 52, 5799. (f) Hansmann, M. M.;
Hashmi, A. S. K.; Lautens, M. Org. Lett. 2013, 15, 3226. (g) Laali,
K. K.; Nandi, G. C.; Borosky, G. L.; Kumar, G. G. K. S. N. Eur. J. Org.
Chem. 2013, 5455. (h) Mattia, E.; Porta, A.; Merlini, V.; Zanoni,
G.; Vidari, G. Chem. Eur. J. 2012, 18, 11894. (i) Pennell, M. N.;
Unthank, M. G.; Turner, P.; Sheppard, T. D. J. Org. Chem. 2011,
76, 1479. (j) Sugawara, Y.; Yamada, W.; Yoshida, S.; Ikeno, T.;
Yamada, T. J. Am. Chem. Soc. 2007, 129, 12902. (k) Engel, D. A.;
Dudley, G. B. Org. Lett. 2006, 8, 4027. (l) Yang, Y. C.; Shen, Y. A.;
Wang, X. L.; Zhang, Y.; Wang, D. W.; Shi, X. D. Tetrahedron Lett.
2016, 57, 2280. (m) Zhu, Y. X.; Sun, L.; Lu, P.; Wang, Y. G. ACS
Catal. 2014, 4, 1911.
(7) (a) Yan, X. Y.; Yi, X. L.; Xi, C. J. Org. Chem. Front. 2014, 1, 657.
(b) Yan, X. Y.; Zou, S.; Zhao, P.; Xi, C. J. Chem. Commun. 2014, 50,
2775. (c) Zhao, P.; Yan, X. Y.; Yin, H.; Xi, C. J. Org. Lett. 2014, 16,
1120. (d) Zhao, P.; Liu, Y.; Xi, C. J. Org. Lett. 2015, 17, 4388.
(e) Liu, Y.; Zhao, P.; Zhang, B.; Xi, C. J. Org. Chem. Front. 2016, 3,
1116. (f) Wang, S.; Shao, P.; Du, G. X.; Xi, C. J. J. Org. Chem. 2016,
81, 6672.
(8) (a) Begue, J. P.; Bonnet-Delpon, D.; Crousse, B. Synlett 2004, 18.
(b) Protti, S.; Fagnoni, M.; Albini, A. Angew. Chem. Int. Ed. 2005,
44, 5675. (c) Abitelli, E.; Protti, S.; Fagnoni, M.; Albini, A. J. Org.
Chem. 2012, 77, 3501. (d) Liu, W. B.; Wang, H. N.; Li, C. J. Org.
Lett. 2016, 18, 2184.
13C NMR (CDCl3, 101 MHz): δ = 199.27, 198.14, 146.81, 137.79,
136.80, 133.11, 132.24, 129.50, 128.63, 128.22, 128.11, 127.26, 37.25,
27.41.
HRMS (ESI): m/z [M + H]+ calcd for C18H17O2+: 265.1223; found:
265.1224.
1-Nitro-4-[1-(2,2,2-trifluoroethoxy)hept-2-ynyl]benzene (2aa)
To a 25 mL round-bottomed flask were added into 1-(4-nitrophe-
nyl)hept-2-yn-1-ol (70 mg, 0.3 mmol), TFE 0.5 mL, and MeOTf (6 μL,
0.06 mmol, 0.2 equiv.). Then the flask was immersed in a 70 °C pre-
heated oil bath and the mixture was stirred for 20 min. After comple-
tion of the reaction, the solution was concentrated and the residue
was subjected to flash chromatography on silica gel with PE/EtOAc as
eluent to afford the desired rearrangement product 2aa as a light yel-
low oil; yield: 0.078 g (83%).
IR (film): 3433, 2958, 2938, 2874, 2225, 1609, 1527, 1494, 1458,
1431, 1352, 1279, 1165, 1109, 971, 854 cm–1
.
1H NMR (CDCl3, 400 MHz): δ = 8.29–8.25 (m, 2 H), 7.75–7.71 (m, 2 H),
5.49 (s, 1 H), 4.05 (qd, J = 8.6, 2.0 Hz, 2 H), 2.35 (td, J = 7.1, 2.0 Hz, 2 H),
1.60–1.54 (m, 2 H), 1.51–1.40 (m, 2 H), 0.96 (t, J = 7.3 Hz, 3 H).
13C NMR (CDCl3, 101 MHz): δ = 148.00, 144.64, 128.12, 123.85 (q, JC,F
=
278.6 Hz). 123.76, 91.91, 74.75, 71.55, 64.95 (q, JC,F = 34.8 Hz), 30.42,
22.00, 18.47, 13.54.
19F NMR (CDCl3, 376 MHz): δ = –73.54.
HRMS (ESI): m/z [M + Na]+ calcd for C15H16F3NO3Na+: 338.0974;
found: 338.0968.
Funding Information
(9) Edens, M.; Boerner, D.; Chase, C. R.; Nass, D.; Schiavelli, M. D.
J. Org. Chem. 1977, 42, 3403.
National Natural Science Foundation of China (21372034)
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–H