Organic Letters
Letter
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(d) Meyer, F.; Dubois, P. CrystEngComm. 2013, 15, 3058. (e) Troff, R.
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(14) See the Supporting Information for the preparation, and the
maximum electrostatic potential (ESP) energy surface of XB donors
bearing different counteranions. The complete copies of NMR charts
and the experimental details are also included in the Supporting
Information.
(15) Although the XB-accepting abilities of TMSBr and TMSI for the
XB donor are not clear, there seemed to be no significant difference
between Br− and I− for their affinities toward the 2-iodoimidazolium
cation; see: (a) Cametti, M.; Raatikainen, K.; Metrangolo, P.; Pilati, T.;
Terraneo, G.; Resnati, G. Org. Biomol. Chem. 2012, 10, 1329. For
discussions on the affinities of XB donors toward halide anions, also
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W.; Makela, T.; Topic, F.; Valkonen, A.; Raatikainen, K.; Rissanen, K.
̈
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Eur. J. Org. Chem. 2013, 1617.
(5) For catalytic activation of sp2-hybridized nitrogen atoms, see:
(a) Bruckman, A.; Pene, M. A.; Bolm, C. Synlett 2008, 900. (b) He,
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(6) For catalytic activation of carbonyl oxygen, see: (a) Coulembier,
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H.; Walter, S. M.; Schindler, S.; Rout, L.; Kniep, F.; Huber, S. M.
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(7) For XB-donor-mediated C−X bond activation, see: (a) Walter, S.
M.; Kniep, F.; Herdtweck, E.; Huber, S. M. Angew. Chem., Int. Ed.
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(8) For the reactions based on XB-donor-catalyzed C−X bond
activation, see: Kniep, F.; Jungbauer, S. H.; Zhang, Q.; Walter, S. M.;
Schinsler, S.; Schnapperelle, I.; Herdweck, E.; Huber, S. M. Angew.
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(17) When a silylether, which might also be generated in situ, was
used as a substrate instead of alcohol 1a, 2a was obtained in only 20%
yield. Therefore, we proposed a more plausible mechanism as shown
in Figure 2.
(9) For the related important examples including XB in the catalytic
system, see: (a) Lindsay, V. N. G.; Lin, W.; Charette, A. B. J. Am.
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(18) In these cases, dimerization of the alcohol was observed,
therefore lowering the chemical yields of 2.
(10) For the reactions cocatalyzed by the TMSCl−InCl3 system, see:
(a) Mukaiyama, T.; Ohno, T.; Nishimura, T.; Han, J. S.; Kobayashi, S.
Bull. Chem. Soc. Jpn. 1991, 64, 2524. (b) Mukaiyama, T.; Ohno, T.;
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(20) Hart, D. W.; Schwartz, J. J. Am. Chem. Soc. 1974, 96, 8115.
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A. J. Org. Chem. 1982, 47, 2125. (b) HN(SO2F)2: Kaur, G.; Kaushik,
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(13) For selected theoretical and experimental studies using
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