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Tetrahedron
ACCEPTED MANUSCRIPT
1-[(4Z)-5-Phenylhepta-1,4-dien-4-yl]pyrrolidin-2-one (8f).
Supplementary content. NMR spectra for all new componds.
Calculations of 1b, 1g, 1f, the resulting vinylzincs and Et2Zn at
the B3LYP/6-31+G(d,p) level of theory. Condensed Fukui’s
functions ꢂꢁ, ꢂꢃ and dual descriptor ꢂ(ꢄ) : table of their values at
O, Cα, and Cβ.
The reaction was conducted on 1-(2-phenylethynyl)pyrrolidin-2-
one (0.25 mmol, 46 mg) 1f according to method B with
diethylzinc (500 µL) and CuI (0.12 mmol, 24 mg, 0.5 equiv) to
1
give 8f as a colorless oil (0.13 mmol, 34 mg, 53%). H NMR
(400 MHz, CDCl3) δ: 0.95 (t, J = 7.5, 3H), 1.63 (quint, J = 7.5,
2H), 2.16 (t, J = 8.0, 2H), 2.46 (q, J = 7.5, 2H), 2.94 (t, J = 6.9,
2H), 3.25 (d, J = 6.7, 2H), 5.08 – 5.04 (dq, J = 10.0 and 1.6 ,1H),
5.14 (dq, J = 17.1 and 1.6, 1H), 5.83 (ddt, J = 16.8, 10.0 and 6.7,
1H), 7.34 – 7.16 (m, 5H). 13C NMR (100 MHz, CDCl3) δ: 13.1
(CH3), 19.4 (CH2), 26.7 (CH2), 31.4 (CH2), 35.0 (CH2), 50.1
(CH2), 116.9 (=CH2), 127.3 (=CH), 128.1 (=CH), 128.4 (=CH),
131.1 (=C), 135.1 (=CH), 140.6 (=C), 141.5 (=C), 175.3 (C=O).
HRMS (ESI): m/z: calcd for [M+H+] C17H22NO: 256.1696, found
256.1696.
References and notes
1
For selected reviews on carbometalation reactions, see : a) Marek, I.;
Chinkov, N.; Banon-Tenne D. Metal-Catalyzed Cross-Coupling
Reactions; De Meijere, A, Diederich, F., Eds; Wiley-VCH, Weinheim,
2004, pp 395-478. b) Didier, D.; Marek I. Copper-catalyzed
Asymmetric Synthesis; Alexakis, A., Krause, N, Woodward, S., Eds;
Wiley-VCH, Weinheim, 2014, pp 267-282. c) Marek, I.; Minko Y.
Metal-Catalyzed Cross-Coupling Reactions and More; De Meijere, A,
Brase, S., Oestreich, M., Eds; Wiley-VCH, Weinheim, 2014, pp 763-
874. d) Muller, D. S.; Marek, I. Chem. Soc. Rev. 2016, 45, 4552-4566.
e) Murakami, K.; Yorimitsu, H. Beilstein J. Org. Chem. 2013, 9, 278-
302.
3-[(2Z)-2-Phenylhexa-2,5-dien-3-yl]-1,3-oxazolidin-2-one
(9b). The reaction was conducted on 3-(2-phenylethynyl)-1,3-
oxazolidin-2-one (0.27 mmol, 50 mg) 1b according to method B
with dimethylzinc (540 µL) and CuI (0.14 mmol, 27 mg, 0.5
equiv) to give 9b as a colorless oil (0.25 mmol, 62 mg, 93%). 1H
NMR (400 MHz, CDCl3) δ: 2.09 (s, 3H), 3.12 (pseudo t, J = 8.6,
2H), 3.30 (d, J = 6.6, 2H), 3.98 (pseudo t, J = 8.6, 2H), 5.12 (dq,
J = 10.0 and 1.6, 1H), 5.19 (dq, J = 16.7 and 1.6, 1H), 5.86 (ddt,
J = 16.7, 10.0 and 6.6, 1H), 7.24-7.36 (m, 5H). 13C NMR (100
MHz, CDCl3) δ: 20.0 (CH3), 35.0 (CH2), 46.6 (CH2), 62.5 (CH2),
117.2 (=CH2), 127.4 (=CH), 127.5 (=CH), 128.6 (=CH), 129.4
(=C), 134.2 (=CH), 136.1 (=C), 141.6 (=C), 157.2 (C=O). HRMS
(ESI): m/z: calcd for [M+H+] C15H18NO2: 244.1332, found
244.1332.
2
3
For general reviews on ynamides, see : a) Evano, G.; Theunissen, C .;
Lecomte, M. Aldrichchim. Acta 2015, 48, 59-70. b) Evano, G;
Michelet, B.; Zhang, C. C. R. Chim. 2016, 1-17. Doi :
10.1016/j.crci.2016.12.002.
a) Chechik-Lankin, H.; Livshin, S.; Marek, I. Synlett 2005, 2098-2010.
b) Das, J. P.; Chechik, H.; Marek, I. Nat. Chem. 2009, 1, 128-132. c)
Minko, Y.; Pasco, M.; Chechik, H.; Marek, I. Beilstein J. Org. Chem.
2013, 9, 526-532. d) Nairoukh, Z.; Kumar, G. G. K. S. N.; Minko, Y.;
Marek, I. Chem. Sci. 2017, 8, 627-630.
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a) Yasui, H.; Yorimitsu, H.; Oshima, K. Bull. Chem. Soc. Jpn. 2008,
81, 373-379. b) Yasui, H.; Yorimitsu, H.; Oshima, K. Chem. Lett.
2007, 36, 32-33.
a) Gourdet, B.; Lam, H. W. J. Am. Chem. Soc. 2009, 131, 3802-3803.
b) Gourdet, B.; Rudkin, M. E.; Watts, C. A.; Lam, H. W. J. Org.
Chem. 2009, 74, 7849-7858. c) Gourdet, B.; Smith, D. L.; Lam, H. W.
Tetrahedron 2010, 66, 6026-6031.
3-[(1Z)-2-phenyl(1-²H)but-1-en-1-yl]-1,3-oxazolidin-2-one
(10b). The reaction was conducted on 3-(2-phenylethynyl)-1,3-
oxazolidin-2-one (0.27 mmol, 50 mg) 1b according to method A
with diethylzinc (540 µL) and CuI (0.14 mmol, 27 mg, 0.5
equiv). The reaction was stirred for 18 h and quenched with
saturated ND4Cl to give 10b as a colorless oil (0.16 mmol, 35
mg, 60%).1H NMR (400 MHz, CDCl3) δ: 0.98 (t, J = 7.4, 3H),
2.36 (q, J = 7.4, 2H), 3.03 (pseudo t, J = 7.9, 2H), 4.12 (pseudo t,
J = 7.9, 2H), 7.16-7.22 (m, 2H), 7.24-7.36 (m, 3H). 13C NMR
(100 MHz, CDCl3) δ: 13.3 (CH3), 30.9 (CH2), 45.2 (CH2), 62.6
(CH2), 119.7 (=CD, t, JD=27), 127.4 (CH), 128.1 (C), 128.2
(CH), 129.3 (CH), 139.2 (=C), 157.4 (C=O). HRMS (ESI): m/z:
calcd for [M+H+] C13H15DNO2: 219.1238, found: 219.1240.
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Takimoto, M.; Gholap, S. S.; Hou, Z. Chem. Eur. J. 2015, 21, 15218-
15223.
Yang, Y. ; Wang, L. ; Jin, Y. ; Zhu, G. Chem. Commun. 2014, 50,
2347-2349.
Sallio, R.; Corpet, M.; Habert, L.; Durandetti, M.; Gosmini, C.;
Gillaizeau, I. J. Org. Chem. 2017, 82, 1254-1259.
For the synthesis of indole derivatives see: a) Couty, S.; Liegault, B.;
Meyer, C.; Cossy, J. Org. Lett. 2004, 6, 2511-2514. b) Frischmuth, A.;
Knochel, P. Angew. Chem. Int. Ed. 2013, 52, 1-6. c) Gati, W.; Couty,
F.; Boubaker, T.; Rammah, M. M.; Rammah, M. B.; Evano, G. Org.
Lett. 2013, 15, 3122-3125. For the synthesis of pyridine derivatives
see: d) Gati, W.; Rammah, M. M.; Rammah, M. B.; Evano, G.
Beilstein J. Org. Chem. 2012, 8, 2214-2222.
(E)-3-(2-phenyl-1-(phenylselanyl)but-1-en-1-yl)oxazolidin-
2-one (11b). The reaction was conducted on 3-(2-
phenylethynyl)-1,3-oxazolidin-2-one (0.27 mmol, 50 mg) 1b
according to method A with diethylzinc (540 µL) and CuI (0.14
mmol, 27 mg, 0.5 equiv). The reaction was stirred for 18 h and
PhSeCl (0.108 mmol, 207 mg) in DCM (0.4 ml) was added at 0
°C. reaction mixture was stirred for 10 h and quenched with
saturated NH4Cl. The layers were separated and the aqueous
layer was extracted with CH2Cl2 (x3). The combined organic
phases were dried over MgSO4, filtered on silica gel and
concentrated under vacuum and purified by flash
chromatography on silica gel (pentane/ether) to give 11b as
colorless oil (0.134 mmol, 50%). NMR (400 MHz, CDCl3) δ:
0.97 (t, J = 7.5 Hz, 3H), 2.76 (q, J = 7.5 Hz, 2H), 3.15 (t, J = 7.7
Hz, 2H), 3.15 (pseudo t, J = 7.7 Hz, 2H), 3.66 (pseudo t, J = 7.6
Hz, 2H), 7.36 – 7.20 (m, 8H), 7.70 – 7.63 (m, 2H). 13C NMR
(100 MHz, CDCl3) δ: 12.7 (CH3), 30.9 (CH2), 46.6 (CH2), 61.9
(CH2), 123.2 (=C), 125.7 (CH), 127.7 (CH), 128.0 (=C), 128.4
(CH), 128.5 (CH), 129.4 (CH), 134.8 (CH), 139.9 (=C), 149.9
(=C), 155.7 (C=O).
10
For selected reviews on the use of iron as catalyst in carbometalation
reactions, see : a) Bolm, C.; Legros, J.; Le Paih, J.; Zani, L Chem. Rev.
2004, 104, 6217-6254. b) Korotvicka, A.; Kotora, M. Iron-mediated
asymmetric synthesis, Chemistry of organoiron compounds; Marek, I.,
Rappoport, Z., Eds; Wiley-VCH, Weinheim, 2014, pp 379-417. For
recent selected examples of iron-catalyzed cabometalation of alkynes,
see: c) Cheung, C. W; Hu, X. Chem. Eur. J. 2015, 21, 18439-18444. d)
Liu, Y.; Wang, L.; Deng, L. J. Am. Chem. Soc. 2016, 138, 112-115.
a) Tarwade, V.; Liu, X.; Yan, N.; Fox, J. M. J. Am. Chem. Soc. 2009,
131, 5382-5383. b) Tarwade, V.; Selvaraj, R.; Fox, J. M. J. Org. Chem.
2012, 77, 9900-9904. c) Muller, D. S.; Marek, I. J. Am. Chem. Soc.
2015, 137, 15414-15417.
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Sklute, G.; Bolm, C.; Marek, I. Org. Lett. 2007, 9, 1259-1261.
The possible role of contaminants in FeCl3-catalyzed coupling
processes has been emphasized, see: Buchwald, S. L. ; Bolm, C.
Angew. Chem. Int. Ed. 2009, 48, 5586-5587. If a copper contaminant
in the iron salt was the effective catalyst, all iron-catalyzed reactions
should be as efficient as copper-catalyzed reactions, which is clearly
not the case (see: Tables 2 and 3). Moreover, all ynamides but 1g were
synthesized according to a copper (II)-catalyzed coupling reaction. The
blank experiment argues against the involvement of a possible copper
contaminant in the substrate.