Page 7 of 8
The Journal of Organic Chemistry
(9)
Allen, B. D.; Cintrat, J.-C.; Faucher, N.; Berthault, P.; Rousseau,
B.; O’Leary, D. J. J. Am. Chem. Soc. 2005, 127 (1), 412–420.
daniel.o’leary@pomona.edu
1
2
3
4
5
6
7
8
Funding Sources
No competing financial interests have been declared.
(10) Restelli, A.; Siegel, J. S. J. Am. Chem. Soc. 1992, 114 (3), 1091–
1092
(11) Lodewyk, M. W.; Siebert, M. R.; Tantillo, D. J. Chem. Rev.
2012, 112 (3), 1839–1862
(12) Halgren, T. A. J. Comput. Chem. 1996, 17 (5-6), 490–519.
(13) Schrodinger Release 2014-3: MacroModel; Schrödinger, LLC:
New York, NY, 2014.
ACKNOWLEDGMENT
O.M.O., D.A.K., S.C., and D.J.O. acknowledge support from
Pomona College. S.J.E., L.J.B., S.S., and M.H.L acknowledge
support from the Engineering and Physical Sciences Re-
search Council (UK), grant codes EP/N002482 and
EP/L505067/1, the Wolfson Foundation, and Bruker Bio-
spin (UK).
(14) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Men-
nucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.;
Hratchian, H. P.; A. F. Izmaylov, A. F.; Bloino, J.; Zheng, G.;
Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.;
Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.;
Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; J. E. Peralta, J. E.;
Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.;
Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.;
Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; To-
masi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J.
E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts,
R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.;
Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.;
Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.;
Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz,
J. V.; Cioslowski, J.; and Fox, D. J. Gaussian, Inc.: Wallingford,
CT, 2009.
(15) Chai, J.-D.; Head-Gordon, M. J. Chem. Phys. 2008, 128 (8),
084106.
(16) Dunning Jr, T. H. J. Chem. Phys. 1989, 90 (2), 1007–1023.
(17) Miertuš, S.; Scrocco, E.; Tomasi, J. Chem. Phys. 1981, 55 (1),
117–129.
(18) Slater, J. C. Phys. Rev. 1951, 81 (3), 385–390.
(19) Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54
(2), 724–728.
(20) Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28 (3),
213–222.
(21) Extensive benchmark of employed theoretical method was
performed. See Supporting Information for more details.
(22) Isotopic NMR shifts calculated using the Onyx program:
Brueckner, A. C.; Cevallos, S. L.; Ogba, O. M.; Walden, D. M.;
Meyer, M. P.; O'Leary, D. J.; Cheong, P. H.-Y. Onyx, version
1.0; Oregon State University: Corvallis, OR, USA & Pomona
College: Claremont, CA, USA, 2016.
(23) See Supporting Information for more details.
(24) Quantum mechanical structures were optimized at 25ºC in
ωB97X/cc-pVTZ/PCM(DCM), NMR single points in HF/6-
311+G(2d,p)/PCM(DCM).
(25) Anet, F. A. L.; Kopelevich, M. J. Chem. Soc., Chem. Commun.
1987, 0 (8), 595–597.
(26) Erxleben, N. D.; Kedziora, G. S.; Urban, J. J. Theor Chem Acc
2014, 133 (7), 1491.
(27) Experimental spectrum was fitted using the Mathematica
based NMR software package SpinDynamica. SpinDynamica
Code for Mathematica, Programmed by Malcolm H. Levitt,
with Contributions by Jyrki Rantaharju, Andreas Brinkmann,
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
REFERENCES
(1)
For recent reviews of LLS, see: (a) Pileio, G.; Prog. Nucl. Magn.
Reson. Spectrosc. 2017, 98–99, 1–19. (b) Levitt, M. H. Annu.
Rev. Phys. Chem. 2012, 63 (1), 89–105.
(2)
(a) Stevanato, G.; Hill-Cousins, J. T.; Hakansson, P.; Roy, S. S.;
Brown, L. J.; Brown, R. C. D.; Pileio, G.; Levitt, M. H. Angew.
Chem. Int. Ed., 2015, 54, 3740-3743. (b) Pileio, G.; Dumez, J.-
N.; Pop, I.-A.; Hill-Cousins, J. T.; Brown, R. C. D. J. Magn. Re-
son. 2015, 252, 130–134. (c) Dumez, J.-N.; Hill-Cousins, J. T.;
Brown, R. C. D.; Pileio, G. J. Magn. Reson. 2014, 246, 27–30.
(d) DeVience, S. J.; Walsworth, R. L.; Rosen, M. S. Phys. Rev.
Lett. 2013, 111 (17), 173002. (e) Feng, Y.; Davis R. M.; War-
ren, W. S. Nat. Phys., 2012, 8, 831-837. (f) Tayler, M. C. D.;
Levitt, M. H. Phys. Chem. Chem. Phys. 2011, 13 (13), 5556–
5560. (g) Pileio, G.; Carravetta, M.; Levitt, M. H. Proc. Natl.
Acad. Sci. 2010, 107 (40), 17135–17139. (h) Warren, W. S.;
Jenista, E.; Branca, R. T.; Chen, X. Science 2009, 323 (5922),
1711–1714. (i) Pileio, G.; Carravetta, M.; Hughes, E.; Levitt, M.
H. J. Am. Chem. Soc., 2008, 130, 12582-12583. (j) Carravetta,
M.; Johannessen, O. G.; Levitt, M. H. Phys. Rev. Lett., 2004,
92, 153003.
(3)
(4)
(a) Ji, X; Bornet, A.; Vuichoud, B.; Milani, J.; Gajan, D.; Rossini,
A. J.; Emsley, L.; Bodenhausen G.; Jannin, S. Nat. Commun.,
2017, 8, 13975. (b) Rodrigues, T. B.; Serrao, E. M.; Kennedy, B.
W. C.; Hu, D.-E.; Kettunen, M. I.; Brindle, K. M. Nat. Med.
2014, 20 (1), 93–97. (c) Ardenkjaer-Larsen, J.-H.; Fridlund, B.;
Gram, A.; Hansson, G.; Hansson, L.; Lerche, M. H.; Servin, R.;
Thaning, M.; Golman, K. Proc. Natl. Acad. Sci. U.S.A., 2003,
100, 10158-10163.
For applications of hyperpolarization, see: (a) Nelson, S. J.;
Kurhanewicz, J.; Vigneron, D. B.; Larson, P. E. Z.; Harzstark, A.
L.; Ferrone, M.; Criekinge, M. van; Chang, J. W.; Bok, R.; Park,
I.; Reed, G.; Carvajal, L.; Small, E. J.; Munster, P.; Weinberg, V.
K.; Ardenkjaer-Larsen, J. H.; Chen, A. P.; Hurd, R. E.; Ode-
gardstuen, L.-I.; Robb, F. J.; Tropp, J.; Murray, J. A. Sci. Transl.
Med. 2013, 5 (198), 198108–198108. (b) DeVience, S. J.; Wal-
sworth, R. L.; Rosen, M. S. NMR Biomed. 2013, 26 (10), 1204–
1212 (c) Bornet, A.; Ahuja, P.; Sarkar, R.; Fernandes, L.; Hadji,
S.; Lee, S. Y.; Haririnia, A.; Fushman, D.; Bodenhausen, G.;
Vasos, P. R. Chemphyschem Eur. J. Chem. Phys. Phys. Chem.
2011, 12 (15), 2729–2734. (d) Ahuja, P.; Sarkar, R.; Vasos, P.
R.; Bodenhausen, G. J. Am. Chem. Soc. 2009, 131 (22), 7498–
7499.
and
Soumya
Singha
Roy.
(28) CYLview, 1.0b; Legault, C. Y., Université de Sherbrooke, 2009
(5)
(6)
(7)
(8)
Elliott, S. J.; Brown, L. J.; Dumez, J.-N.; Levitt, M. H. Phys.
Chem. Chem. Phys. 2016, 18 (27), 17965–17972.
Elliott, S. J.; Brown, L. J.; Dumez, J.-N.; Levitt, M. H. J. Magn.
Reson. 2016, 272, 87–90.
Anet, F. A. L.; Kopelevich, M. J. Am. Chem. Soc. 1989, 111 (9),
3429–3431.
Allen, B. D.; O’Leary, D. J. J. Am. Chem. Soc. 2003, 125 (30),
9018–9019.
(29) (a) Sandoval-Lira, J.; Fuentes, L.; Quintero, L.; Höpfl, H.; Her-
nández-Pérez, J. M.; Terán, J. L.; Sartillo-Piscil, F. J. Org. Chem.
2015, 80 (9), 4481–4490. (b) Scheiner, S. Phys. Chem. Chem.
Phys. 2011, 13 (31), 13860–13872 (c) Cannizzaro, C. E.; Houk,
K. N. J. Am. Chem. Soc. 2002, 124 (24), 7163–7169. (d) Corey,
E. J.; Rohde, J. J. Tetrahedron Letters 1997, 38 (1), 37–40. For
CH•••O reviews, see: (e) Desiraju, G. R. Acc. Chem. Res. 1996,
ACS Paragon Plus Environment