10.1002/adsc.201900788
Advanced Synthesis & Catalysis
Representative procedure for the synthesis of
diarylamines from 1,3,5-trimethoxybenzene and
nitrosobenzene: An oven-dried glass vial is charged with
a magnetic stir bar, 1a (75.0 mg, 0.45 mmol, 3.0 equiv),
and 2a (16.0 mg, 0.15 mmol, 1.0 equiv). 1,1,1,3,3,3-
Hexafluoro-2-propanol (HFIP) (0.2 mL, 0.15 M) is added
to the mixture in argon atmosphere. The vial is maintained
for 40 h at 55oC. The reaction mixture is then passed
through a plug of silica. The vial is rinsed with CH2Cl2 (2
X 2 mL), and the collected organic phases are evaporated
under reduced pressure. The analytically pure product 3a is
obtained by column chromatography on silica gel using
petroleum ether and ethyl acetate (20:1, v/v) as eluent.
[4] Selected reports on FC reaction with benzylic
systems: a) P. A. Champagne, Y. Benhassine, J.
Desroches, Paquin; Angew. Chem. Int. Ed. 2014, 53,
1383–13839; b) N. Weisner, M. G. Khaledi, Green
Chem. 2016, 18, 681–685; c) V. D. Vuković, E.
Richmond, E. Wolf, J. Moran, Angew. Chem. Int. Ed.
2017, 56, 3085–3089.
[5] Selected report on FC reaction with epoxides: a) G.-X.
Li, J. Qu, Chem. Commun. 2010, 46, 2653–2655; b)
Y. Tian, X. Xu, L. Zhang, J. Qu, Org. Lett. 2016, 18,
268–271.
Representative procedure for the synthesis of
iminoquinone
from
1,3,5-trimethoxybenzene,
[6] Selected reports on FC reaction with cyclopropane:
a)E. Richmond, V. D. Vuković, J. Moran, Org. Lett.
2018, 20, 574–577; b) E. Richmond, J. Yi, V. D.
Vuković, F. Sajadi, C. N. Rowley, J. Moran, Chem.
Sci. 2018, 9, 6411–6416.
nitrosobenzene and TfOH as an additive: An oven-dried
glass vial is charged with a magnetic stir bar, 1a (25.0 mg,
0.15 mmol, 1.0 equiv), and 2a (48.0 mg, 0.45 mmol, 3.0
equiv). A solution of TfOH (150.0 µl, 20 mol%, 0.2 M in
HFIP) in 1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP) (50.0
µl, 0.75 M) is added to the mixture. The vial is maintained
o
for 12 h at 40 C.The reaction mixture is then passed
[7] For a recent review on HFIP as a solvent, see: a) I.
Colomer, A. E. R. Chamberlain, M. B. Haughey, T. J.
Donohoe, Nat. Rev. Chem. 2017, 1, 1–12 and
references cited thereafter; b) S. K. Sinha, T.
Bhattacharya, D. Maiti, React. Chem. Eng. 2019, 4,
244–253.
through a plug of silica. The vial is rinsed with CH2Cl2 (2
X 2mL), and the collected organic phases are evaporated
under reduced pressure. The analytically pure product 4a is
obtained by column chromatography on silica gel using
petroleum ether and ethylacetate (1:1, v/v) as eluent.
Representative procedure for the synthesis of
iminoquinone from p-xylene and nitrosobenzene: An
oven-dried glass vial is charged with a magnetic stir bar, p-
xylene (90.0µl, 0.75 mmol, 5.0 equiv), and 2a (16.0 mg,
0.15 mmol, 1.0 equiv). 1,1,1,3,3,3-Hexafluoro-2-propanol
(HFIP) (0.2 mL, 0.75 M) is added to the mixture in argon
atmosphere. The vial is maintained for 40 h at 55oC. The
reaction mixture is then passed through a plug of silica.
The vial is rinsed with CH2Cl2 (2 X 2 mL), and the
collected organic phases are evaporated under reduced
pressure. The analytically pure product 8a is obtained by
column chromatography on silica gel using petroleum
ether and ethyl acetate (40:1, v/v) as eluent.
[8] Selected reports on HFIP mediated C–H amination:
a) R. -J. Tang, T. Milcent, B. Crousse, Eur. J. Org.
Chem. 2017, 4753–4757; b) Nitrosopyridine was used
for the annulation reaction with alkynes in HFIP; S.
Manna, R. Narayan, C. Golz, C. Strohmann, A. P.
Antonchick, Chem. Commun. 2015, 51, 6119–6122.
[9] For the synthesis of diarylamines using
nitrosobenzene and arene based organometallics
reagents see: a) Y. Yu, J. Srogl, L. S. Liebeskind,
Org. Lett. 2004, 6, 2631–2634;b) B. Zhou, J. Du, Y.
Yang, H. Feng, Y. Li, Org. Lett. 2013,15, 6302–
6305; c) J. Du, Y. Yang, H. Feng, Y. Li, B. Zhou,
Chem.–Eur. J. 2014, 20, 5727–5731; d) V. Dhayalan,
C. Sämann, P. Knochel, Chem. Commun. 2015, 51,
3239–3242; e) S. Roscales, A. G. Csákÿ, Org. Lett.
2018, 20, 1667–1671.
Acknowledgements
The authors wish to acknowledge financial assistance from
Indian Institute of Technology, Ropar and SERB, DST, India
(ECR/2018/000098). S.P., S. R. and S.G. thank IIT Ropar and
UGC, New Delhi, respectively, for their research fellowships.
[10] J. Börgel, L. Tanwar, F. Berger, T. Ritter, J. Am.
Chem. Soc. 2018, 140, 16026−16031.
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