10.1002/ejoc.201801323
European Journal of Organic Chemistry
FULL PAPER
aqueous) in MeCN. The fractions containing the product were
collected and concentrated in vacuo. The concentrate was taken
up in Et2O (20 mL) and washed with 2M NaOH (20 mL). The
organics were separated, dried over MgSO4, filtered, and
concentrated in vacuo to give 72 mg (63% yield) of a colorless oil.
1H NMR (400 MHz, Benzene-d6) δ 7.49 (d, J = 7.1 Hz, 2H), 7.25
(dd, J = 8.4, 6.9 Hz, 2H), 7.15 – 7.10 (m, 1H), 3.71 (q, J = 6.7 Hz,
1H), 2.92 – 2.51 (m, 13H), 1.31 (d, J = 6.7 Hz, 3H), 1.03 (s, 9H),
0.95 (d, J = 2.0 Hz, 3H), 0.94 (d, J = 2.0 Hz, 3H). 13C NMR (100
MHz, Chloroform-d) δ 146.00, 128.00, 127.97, 126.34, 63.01,
54.98, 54.33, 53.61, 53.56, 53.06, 53.04, 52.30, 51.50, 27.11,
18.92, 18.28, 17.90. Positive Mode NSI-MS m/z: exact mass
References
[1]
a) P. Chaudhuri, K. Wieghardt. Prog. Inorg. Chem. 1987,
35, 329; b) K. P. Wainwright. Coord. Chem. Rev. 1997,
166, 35-90; c) R. I. Haines. Rev. Inorg. Chem. 2001, 21,
165-206.
[2]
a) R. Hage, J. E. Iburg, J. Kerschner, J. H. Koek, E. L. M.
Lempers, R. J. Martens, U. S. Racherla, S. W. Russell, T.
Swarthoff, M. R. P. van Vliet, J. B. Warnaar, L. v. d. Wolf,
B. Krijnen. Nature 1994, 369, 637-639; b) R. Hage, J. W.
de Boer, F. Gaulard, K. Maaijen, in Adv. Inorg. Chem.,
Vol. 65 (Eds.: R. van Eldik, C. D. Hubbard), Academic
Press, 2013, pp. 85-116.
+
calculated for C21H38N3 ([M+H]+): 332.30602; found 332.30654
[3]
[4]
J. E. Richman, T. J. Atkins. J. Am. Chem. Soc. 1974, 96,
2268-2270.
( = 1.6 ppm).
a) N. Luk'yanenko, S. Basok, L. Filonova, N. Kulikov, V.
Pastushok. Chem. Heterocycl. Compd. 1990, 26, 346-349;
b) J. F. Wei, X. Y. Shi, D. P. He, Y. Zhang. Chinese J.
Org. Chem. 2003, 23, 1142-1145; c) P. Désogère, Y.
Rousselin , S. Poty, C. Bernhard, C. Goze, F. Boschetti, F.
Denat. Eur. J. Org. Chem. 2014, 2014, 7831-7838; d) S.
A. Madison, D. J. Batal, Lever Brothers Co, U.S. Pat.
5,284,944, 1994.
[Cu(tBu2menthyltacn)(MeCN)]PF6. To a scintillation vial in the
glovebox containing 1,4-di-tert-butyl-7-((1S,2S,5R)-2-isopropyl-5-
methylcyclohexyl)-1,4,7-triazacyclononane (165 mg, 0.435 mmol,
1.0
equiv)
was
added
tetrakisacetonitrile
copper(I)
hexafluorophosphate (165 mg, 0.442 mmol, 1.0 equiv) as a
solution in THF (5 mL). The mixture was stirred for two hours at
room temperature, then concentrated in vacuo. The crude
concentrate was purified by crystallization from THF/pentane
vapor diffusion to give 96 mg (33% yield) of colorless crystals
suitable for x-ray diffraction. 1H NMR (400 MHz, Acetonitrile-d3) δ
3.27 (dt, J = 12.9, 4.5 Hz, 1H), 3.18 – 3.05 (m, 2H), 3.03 – 2.90
(m, 4H), 2.86 – 2.69 (m, 3H), 2.62 – 2.45 (m, 2H), 2.31 (tdd, J =
10.6, 4.8, 2.7 Hz, 2H), 2.23 – 1.99 (m, 3H), 1.79 – 1.65 (m, 3H),
1.58 (dt, J = 14.3, 5.3 Hz, 1H), 1.25 (s, 9H), 1.24 (s, 9H), 1.07 (d,
J = 6.9 Hz, 3H), 1.04 (d, J = 6.9 Hz, 3H), 0.94 (d, J = 6.7 Hz, 4H).
13C NMR (100 MHz, Acetonitrile-d3) δ 64.87, 59.41, 59.32, 57.76,
53.57, 52.76, 47.80, 47.65, 47.24, 41.77, 35.47, 29.12, 29.00,
27.74, 27.15, 24.30, 21.95, 20.87, 18.99. See supporting
information: Figure S37 for powder XRD.
[5]
[6]
a) G. R. Weisman, D. J. Vachon, V. B. Johnson, D. A.
Gronbeck. J. Chem. Soc., Chem. Commun. 1987, 886-
887; b) I. Lázár, Z. Takács. Synth. Commun. 2001, 31,
3141-3144; c) H. S. Winchell, J. Y. Klein, E. D. Simhon,
R. L. Cyjon, O. Klein, H. Zaklad, U.S. Pat. 5874573 A,,
1999.
a) C. Bolm, D. Kadereit, M. Valacchi. Synlett 1997, 1997,
687-688; b) G. Argouarch, C. L. Gibson, G. Stones, D. C.
Sherrington. Tetrahedron Lett. 2002, 43, 3795-3798; c) C.
Bolm, N. Meyer, G. Raabe, T. Weyhermuller, E. Bothe.
Chem. Commun. 2000, 2435-2436; d) S. Pulacchini, K. F.
Sibbons, K. Shastri, M. Motevalli, M. Watkinson, H. Wan,
A. Whiting, A. P. Lightfoot. Dalton Trans. 2003, 2043-
2052; e) G. Stones, G. Argouarch, A. R. Kennedy, D. C.
Sherrington, C. L. Gibson. Org. Biomol. Chem. 2003, 1,
2357-2363; f) G. Stones, R. Tripoli, C. L. McDavid, K.
Roux-Duplâtre, A. R. Kennedy, D. C. Sherrington, C. L.
Gibson. Org. Biomol. Chem. 2008, 6, 374-384; g) V. B.
Romakh, B. Therrien, G. Süss-Fink, G. B. Shul'pin. Inorg.
Chem. 2007, 46, 1315-1331.
[Cu(tBu2sec-PhEttacn)(NCPh)]OTf. To a scintillation vial in the
glovebox containing (S)-1,4-di-tert-butyl-7-(1-phenylethyl)-1,4,7-
triazacyclononane (186 mg, 0.538 mmol, 1.0 equiv) and MeCN (~
4 mL) was added tetrakisacetonitrile copper(I) triflate (203 mg,
0.538 mmol, 1.0 equiv). The mixture was stirred overnight at room
temperature, then concentrated in vacuo. The crude concentrate
was taken up in a minimum quantity of benzonitrile, and vapor
diffused with a mixture of Et2O and pentane to give 220 mg (64%
yield) of yellow needles suitable for x-ray diffraction. 1H NMR (300
MHz, Acetonitrile-d3) δ 7.84 – 7.25 (m, 10H), 3.97 (q, J = 6.8 Hz,
1H), 3.13 – 2.82 (m, 6H), 2.67 – 2.31 (m, 6H), 2.30 – 2.15 (m, 1H),
1.64 (d, J = 6.8 Hz, 3H), 1.26 (s, 9H), 1.20 (s, 9H). 13C NMR (75
MHz, Acetonitrile-d3) δ 141.38, 133.98, 133.10, 130.21, 130.05,
129.17, 129.00, 112.94, 67.41, 59.42, 59.36, 56.52, 51.41, 51.04,
50.34, 48.92, 48.29, 26.94, 20.44. Nitrile carbon 13C resonance
not observed. Anal. calc. for: C30H44CuF3N4O3S: C, 54.49; H,
6.71; N, 8.47. Found: C, 54.55; H, 6.53; N, 8.43.
[7]
[8]
a) J. Robb, R. D. Peacock. Inorg. Chim. Acta 1986, 121,
L15-L17; b) P. Rossi, F. Felluga, P. Scrimin. Tetrahedron
Lett. 1998, 39, 7159-7162.
a) J. E. W. Scheuermann, F. Ronketti, M. Motevalli, D. V.
Griffiths, M. Watkinson. New J. Chem. 2002, 26, 1054-
1059; b) M. Beller, A. Tafesch, R. W. Fischer, B.
Scharbert, German Pat. 19523891, 1995; c) B. M. Kim, S.
M. So, H. J. Choi. Org. Lett. 2002, 4, 949-952; d) J. Koek,
E. Kohlen, S. Russell. Inorg. Chim. Acta 1999, 295, 189-
199; e) P. Graham, D. Weatherburn. Aust. J. Chem.
1983, 36, 2349-2354; f) J. P. L. Cox, A. S. Craig, I. M.
Helps, K. J. Jankowski, D. Parker, M. A. W. Eaton, A. T.
Millican, K. Millar, N. R. A. Beeley, B. A. Boyce. J. Chem.
Soc., Perkin Trans. 1 1996, 2567–2576; g) S. W. Golding,
T. W. Hambley, G. A. Lawrence, S. M. Luther, M. Maeder,
P. J. Turner. Chem. Soc., Dalton Trans. 1999, 1975–1980;
h) J. E. W. Scheuermann, K. F. Sibbons, D. M. Benoit, M.
Motevalli, M. Watkinson. Org. Biomol. Chem 2004, 2,
2664-2670; i) A. F. Drake, R. Kuroda, S. F. Mason. J.
Chem. Soc., Dalton Trans. 1979, 1095-1100; j) M.
Nonoyama. Transition Met. Chem. 1980, 5, 269-271; k) S.
Kamioka, S. Sugiyama, T. Takahashi, T. Doi. Org. Biomol.
Chem. 2010, 8, 2529-2536.
Acknowledgements
Financial support was provided by the Donors of the American
Chemical Society Petroleum Research Fund and Emory
University for supporting this research.
Keywords
Synthetic methods · Nitrogen heterocycles · Macrocyclic
polyamines · Chelates
[9]
K. Wieghardt, P. Chaudhuri, B. Nuber, J. Weiss. Inorg.
Chem. 1982, 21, 3086-3090.
[10]
A. Thangavel, M. Wieliczko, J. Bacsa, C. C. Scarborough.
Inorg. Chem. 2013, 52, 13282-13287.
This article is protected by copyright. All rights reserved.