Page 13 of 15
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Lawrence B. Alemany (Rice University) for the acquisition
5473ꢀ5476.
1
2
3
4
and analysis of 29 fluorine NMR spectra. We also thank G.
Bellavance, T. Benkovics, S. E. Denmark, Z.G. Hajos, M.M.
Joullié, O. Larionov, J. Lopchuk, I. Marek, K.C. Nicolaou, J. T.
Njardarson, M. Pavia, E. Pitsinos, D. Richter, D. Rhoades, S.
Rigol, A. Toro and D. Vourloumis for helpful commentary.
34. Nohira, H.; Sato, K.; Mukaiyama, T., Bull. Chem. Soc. Jpn. 1963,
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5
6
7
8
9
37. A thorough solvent study (see the SI on page S58) revealed that
while Nꢀattack was favored for imine 40, the proportion of the Cꢀ
attack product was generally high (e.g., 53% Nꢀattack along with
32% of Cꢀattack product in DCM/THF). In addition, the cost of diꢀ
tertꢀbutyl malonate (38) is significantly more than that of diꢀ
isopropyl malonate (37) and also the preparation of the diol 44 from
37 proceeds with better efficiency than the corresponding diol from
38 (52% versus 68%, see the SI for more details).
38. Sivan, A.; Deepthi, A., Tetrahedron Lett. 2014, 55, 1890ꢀ1893.
39. Tietze, L. F.; Bratz, M., Org. Synth. 1993, 71, 214ꢀ19.
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41. Differential scanning calorimetry (DSC) data were collected and
analyzed (see the SI) on all of the aminating agents described in this
manuscript to assess their thermal stability and evaluate their safety.
The DSC data were collected on a TA Instruments Q1000 equipped
with a RSC90 (refrigerated cooling system) using sealed standard
aluminum hermetic pans (note for more rigorous safety evaluation,
we recommend the use of goldꢀplated high pressure crucibles, and
hence only onset temperatures are reported in the SI), and the
samples were crimped closed. The typical ramp tests were conducted
using the following parameters: hold sample at 30 °C for 10 minutes
followed by a ramp from 30 °C to 300 °C at 10 °C/min.
42. A thorough literature search revealed that there is dearth of methods
for the preparation of symmetrical diarylamines as only three
relevant papers were found on this topic: (a) K. Taniguchi, X. Jin, K.
Yamaguchi, K. Nozaki, N. Mizuno, Chem. Sci. 2017, 8, 2131ꢀ2142;
(b) A. Tlili, F. Monnier, M. Taillefer, Chem. Commun. 2012, 48,
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D. A. Aksenov, M. V. Dmitriev, M. Rubin, RSC Adv. 2015, 5,
84849ꢀ84855. In contrast, the preparation of unsymmetrical
diarylamines is the subject of hundreds of papers.
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