A. Kumar, A. G. Samuelson
FULL PAPER
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NMR (100 MHz, CDCl3, 25 °C): δ = 49.50, 56.12, 114.63, 115.41,
127.75, 128.11, 129.23, 140.56, 143.14, 152.65 ppm.
N-(2-Methoxyphenyl)benzenemethanamine
(3g):
1H
NMR
(400 MHz, CDCl3, 25 °C): δ = 7.3 (m, 5 H), 6.82 (m, 2 H), 6.72
(m, 1 H), 6.61 (m, 1 H), 4.36 (s, 2 H), 3.86 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3, 25 °C): δ = 48.51, 55.89, 110.06, 112.10, 116.66,
117.36, 121.53, 127.98, 128.66, 137.73, 140.76, 147.27 ppm.
2-Hydroxy-3-methoxy-N-phenylbenzenemethanamine
(3h):
1H
[6]
NMR (400 MHz, CDCl3, 25 °C): δ = 7.09 (t, J = 8.0 Hz, 4 H), 6.73
(m, 4 H), 4.29 (s, 2 H), 3.80 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3, 25 °C): δ = 44.71, 56.51, 110.41, 114.20, 118.61, 120.00,
121.09, 129.68, 144.56, 147.22, 148.59 ppm. HRMS: calcd. for
C14H15NNaO2 [M + Na]+ 252.1000; found 252.1000.
2-Hydroxy-N-phenylbenzenemethanamine (3i): 1H NMR (400 MHz,
CDCl3, 25 °C): δ = 8.18 (s, 1 H), 7.28 (m, 5 H), 6.97 (m, 4 H), 4.45
(s, 2 H) ppm. 13C NMR (100 MHz, CDCl3, 25 °C): δ = 46.37,
112.61, 115.36, 116.05, 119.23, 126.20, 127.99, 128.64, 129.33,
149.38, 155.41 ppm.
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Computational Details: For theoretical studies, the imine 1a, tita-
nium intermediates 8, 9, 12, and 13 were modeled. All structures
were optimized using DFT (B3LYP/LANL2DZ)/UFF molecular
mechanics calculations. The multilayer ONIOM model was used
where the Ti, N, O, and C atoms (involved in C–C coupling and
methine C atom of isopropoxide) were considered as the high layer
and the rest of the atoms were defined as a low layer (see the Sup-
porting Information). Atoms considered as high layer are repre-
sented as “ball and stick”, whereas atoms in the low layer are repre-
sented as “tubes”. The high layer was optimized using DFT at the
B3LYP/LANL2DZ level of theory and the low layer was optimized
using molecular mechanics calculation with the UFF forcefield.
The Gaussian 09 program package was used for all calculations.[20]
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Supporting Information (see footnote on the first page of this arti-
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Acknowledgments
A. G. S. thanks the Department of Biotechnology (DBT), New
Delhi for the award of a research grant and A. K. gratefully ac-
knowledges a senior research fellowship from the Council of Scien-
tific and Industrial Research (CSIR) and a PDF from the Indian
Institute of Science (IISc), Bangalore. We also thank S. Dinda for
her help with Gaussian calculations. We thank the Department of
Science and Technology (DST), New Delhi, for providing us funds
through its FIST program for purchase of a 400 MHz NMR spec-
trometer.
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