Journal of the American Chemical Society
Article
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(14) (a) Similarly to the structure of 4a, chemical shift for
(PhO)2P(O)(OTMS) in 31P NMR is assigned as −20.8 ppm, see:
Chojnowski, J.; Cypryk, M.; Michalski, J.; Wozniak, L. J. Organomet.
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Chem. 1985, 288, 275. (b) EI-MS (4a): m/z = 382 (M+; 70 eV; 40%),
367 (8%), 337 (100%), 309 (32%), 291 (26%), 277 (11%), 261
(44%), 233 (31%), 215 (61%), 201 (9%), 170 (8%), 151 (9%), 123
(15%), 105 (3%), 91 (4%), 77 (26%), 51 (4%). Intermediate 4a is
sensitive to moisture and temperature. Although many attempts were
carried out to isolate 4a by silica gel chromatography and high-vacuum
distillation under Ar, color change was always observed and
(EtO)3SiMe was the major compound obtained through decom-
position of 4a. (c) The formation of phosphoric silyl esters from
phosphoric acids and hydrosilanes is supported by the formation of
silyl ethers from alcohols and hydrosilanes in the presence of Lewis
aicds, see: Sridhar, M.; Raveendra, J.; Ramanaiah, B. C.; Narsaiah, C.
Tetrahedron Lett. 2011, 52, 5980. (d) Both Lewis basic ‘PO’ and
Lewis acidic ‘Si’ sites in intermediates 4 are believed to be the key for
its unique reactivity for reduction of phosphine oxides compared to
other acids. (e) For silyl esters, such as TMSOTf as Lewis acid
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Pehlivan, L.; Metay, E.; Delbrayelle, D.; Mignani, G.; Lemaire, M.
Tetrahedron 2012, 68, 3151.
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(15) (a) For details, see the Supporting Information. (b) Under the
same conditions, no reactivity was observed for reduction of [4-(N,N-
dimethylamino)phenyl]diphenylphosphine oxide.
(16) For selective reduction of ketones and esters in the presence of
aldehydes, see: Bastug, G.; Dierick, S.; Lebreux, F.; Marko,
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I. E. Org.
(17) Conditions for Cu(OTf)2 catalyzed reduction of phosphine
oxide: 0.25 mol of the substrate, 10 mol % of Cu(OTf)2 and 300 mol
% of tertramethyldisiloxane (TMDS) compared to each PO, 100
°C, 24 h, toluene (2−6 mL).
(18) (a) Performing a Scifinder search using the key words
“phosphine oxide reduction” gave about 250 publications since year
2000 which demonstrates the general interest in this area.
(19) For the use of phosphines with reducible groups, such as ketone,
aldehyde, imine, olefin groups, see: (a) Mikami, K.; Wakabayashi, K.;
Aikawa, K. Org. Lett. 2006, 8, 1517. (b) Jing, Q.; Sandoval, C. A.;
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A.; Mohamad, J.; Mignani, G.; Docherty, G.; Lemaire, M. Synlett 2007,
1545. (f) Petit, C.; Favre-Reguillon, A.; Albela, B.; Bonneviot, L.;
Mignani, G.; Lemaire, M. Organometallics 2009, 28, 6379. (g) Petit, C.;
Favre-Reguillon, A.; Mignani, G.; Lemaire, M. Green Chem. 2010, 12,
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M. A.; Hernandez, R.; Ibarlucea, L.; Pinilla, E.; Torres, M. R.;
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M.-X.; Wang, F.-J.; Shi, M. J. Organomet. Chem. 2011, 2850.
(g) Shintani, R.; Duan, W.; Nagano, T.; Okada, A.; Hayashi, T.
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(20) (a) van Kalkeren, H. A.; Leenders, S. H. A. M.; Hommersom, C.
R. A.; Rutjes, F. P. J. T.; van Delft, F. L. Chem.Eur. J. 2011, 17,
11290. (b) van Kalkeren, H. A.; Bruins, J. J.; Rutjes, F. P. J. T.; van
Delft, F. L. Adv. Synth. Catal. 2012, 354, 1417.
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(10) (a) Li, Y.; Das, S.; Zhou, S.; Junge, K.; Beller, M. J. Am. Chem.
Soc. 2012, 134, 9727. (b) If bisphosphine oxides were the substrates in
Cu(OTf)2/TMDS system, the colour of reaction solution became dark
brown in stead of being colourless for monophosphine oxides (also see
the results in Table 5).
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D. J.; Blachwell, J. M.; Piers, W. E. J. Org. Chem. 2000, 65, 3090.
(b) Malkov, A. V.; Liddon, A. J. P. S.; Ramírez-Lop
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