Journal of the American Chemical Society
Page 8 of 10
Gearing Dynamics. J. Am. Chem. Soc. 2010, 132, 7828-7829. (c)
(7) (a) Scott, V. J.; Remle, Ç.-Ç.; Ozerov, O. V. Room-Temperature
Romanato, P.; Duttwyler, S.; Linden, A.; Baldridge K. K.; Siegel, J. S.
Competition between π-Arene and Lone-Pair Halogen
Coordination of Silylium Ions ? J. Am. Chem. Soc. 2011, 133, 11844-
11846. (d) Chauhan, M.; Chuit, C.; Corriu, R. J. P.; Mehdi, A.; Reyé, C.
Study of Silyl Cations Bearing an Aryldiamine Pincer Ligand
Organometallics, 1996, 15, 4326-4333. (e) Müller, T. A Silyl Cation
with a Three-Center Si-H-Si Bond. Angew. Chem. Int. Ed. 2001, 40,
3033-3036. (f) Khalimon, A. Y.; Lin, Z. H.; Simionescu, R.;
Vyboishchikov, S. F.; Nikonov, G. I. Persistent Silylium Ions
Stabilized by Polyagostic Si-H⋅⋅⋅Si Interactions. Angew. Chem. Int.
Ed. 2007, 46, 4530-4533. (g) Lehmann, M.; Schulz, A.; Villinger, A.
Bissilylated Halonium Ions: [Me3Si-X-SiMe3][B(C6F5)4] (X=F, Cl, Br,
I). Angew. Chem. Int. Ed. 2009, 48, 7444-7447. (h) Müther, K.;
Fröhlich, R.; Mück-Lichtenfeld, C.; Grimme, S.; Oestreich, M. A
Unique Transition Metal-Stabilized Silicon Cation. J. Am. Chem. Soc.
2011, 133, 12442-12444. (i) Ibad, M. F.; Langer, P.; Schulz, A.;
Villinger, A. Silylium-Arene Adducts: An Experimental and
Theoretical Study. J. Am. Chem. Soc. 2011, 133, 21016-21027. (j)
Müther, K.; Hrobarik, P.; Hrobarikova, V.; Kaupp, M.; Oestreich, M.
The Family of Ferrocene-Stabilized Silylium Ions: Synthesis, 29Si
NMR Characterization, Lewis Acidity, Substituent Scrambling, and
Quantum-Chemical Analyses. Chem. Eur. J. 2013, 19, 16579-16594.
(k) Reißmann, M.; Schäfer, A.; Panisch, R.; Schmidtmann, M.; Bolte,
M.; Müller, T. Cyclic Silylated Onium Ions of Group 15 Elements.
Inorg. Chem. 2015, 54, 2393-2402. (l) Rohde, V. H. G.;
Pommerening, P.; Klare, H. F. T.; Oestreich, M. Intramolecularly
Sulfur-Stabilized Silicon Cations as Lewis Acid Catalysts.
Organometallics 2014, 33, 3618-3628. (m) Albers, L.; Aghazadeh
Meshgi, M.; Baumgartner, J.; Marschner, C.; Müller, T.
Wagner−Meerwein-Type Rearrangements of Germa-polysilanes -
A Stable Ion Study. Organometallics 2015, 34, 3756-3763. (n)
Chen, Q.-A.; Klare, H. F. T.; Oestreich, M. Brønsted Acid-Promoted
Formation of Stabilized Silylium Ions for Catalytic Friedel−Crafts
C−H Silylation. J. Am. Chem. Soc. 2016, 138, 7868-7871. (o) Arii, H.;
Yano, Y.; Nakabayashi, K.; Yamaguchi, S.; Yamamura, M.; Mochida,
K.; Kawashima, T. Regioselective and Stereospecific
Dehydrogenative Annulation Utilizing Silylium Ion-Activated
Alkenes. J. Org. Chem. 2016, 81, 6314-6319.
Catalytic Hydrodefluorination of C(sp3)-F Bonds. J. Am. Chem. Soc.
2005, 127, 2852-2853. (b) Douvris, C.; Ozerov, O. V.
Hydrodefluorination of Perfluoroalkyl Groups Using Silylium-
Carborane Catalysts. Science, 2008, 321, 1188-1190. (c) Douvris,
C.; Nagaraja, C. M.; Chen, C.-H.; Foxman, B. M.; Ozerov, O. V.
Hydrodefluorination and Other Hydrodehalogenation of Aliphatic
Carbon-Halogen Bonds Using Silylium Catalysis. J. Am. Chem. Soc.
2010, 132, 4946-4953. (d) Panisch, R.; Bolte, M.; Müller, T.
Hydrogen- and Fluorine-Bridged Disilyl Cations and Their Use in
Catalytic C-F Activation. J. Am. Chem. Soc. 2006, 128, 9676-9682.
(e) Lühmann, N.; Hirao, H.; Shaik, S.; Müller, T. Disilylfluoronium
Ions-Synthesis, Structure, and Bonding. Organometallics 2011, 30,
4087-4096. (f) Lühmann, N.; Panisch, R.; Müller, T. A catalytic C-C
bond-forming reaction between aliphatic fluorohydrocarbons and
arylsilanes. Appl. Organomet. Chem. 2010, 24, 533-537. (g)
Allemann, O.; Duttwyler, S.; Baldridge, K. K.; Siegel, J. S. Proton-
Catalyzed, Silane-Fueled Friedel-Crafts Coupling of Fluoroarenes.
Science 2011, 332, 574-577. (h) Stahl, T.; Klare, H. F. T.; Oestreich,
M. Main-Group Lewis Acids for C−F Bond Activation. ACS Catal.
2013, 3, 1578-1587. (i) Kordts, N.; Künzler, S.; Rathjen, S.; Sieling,
T.; Großekappenberg, H.; Schmidtmann, M.; Müller, T. Silyl
Chalconium Ions: Synthesis, Structure and Application in
Hydrodefluorination Reactions. Chem. Eur. J. 2017, 23, 10068-
10079. (j) Mallov, I.; Ruddy, A. J.; Zhu, H.; Grimme, S.; Stephan, D. W.
C-F Bond Activation by Silylium Cation/Phosphine Frustrated
Lewis Pairs: Mono-Hydrodefluorination of PhCF3, PhCF2H and
Ph2CF2. Chem. Eur. J. 2017, 23, 17692-17696.
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4
5
6
7
8
9
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11
12
13
14
15
16
17
18
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24
25
26
27
28
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30
31
32
33
34
35
36
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38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(8) (a) Schäfer, A.; Reißmann, M.; Schäfer, A.; Saak, W.; Haase, D.;
Müller T. A New Synthesis of Triarylsilylium Ions and Their
Application in Dihydrogen Activation. Angew. Chem. Int. Ed. Engl.,
2011, 50, 12636-12638. (b) Reißmann, M.; Schäfer, A.; Jung, S.;
Müller, T. Silylium Ion/Phosphane Lewis Pairs. Organometallics
2013, 32, 6736-6744.
(9) (a) Omann, L.; Qu, Z.-W.; Irran, E.; Klare, H. F. T.; Grimme, S.;
Oestreich, M. Electrophilic Formylation of Arenes by Silylium Ion
Mediated Activation of Carbon Monoxide. Angew. Chem. Int. Ed.
2018, 57, 8301-8305. (b) Devillard, M.; de Bruin, B.; Siegler, M. A.;
van der Vlugt, J. I. Transition-Metal-Free Cleavage of CO. Chem. Eur.
J. 2017, 23, 13628-13632.
(10) (a) Schmidt, R. K.; Klare, H. F. T.; Fröhlich, R.; Oestreich, M.
Planar Chiral, Ferrocene-Stabilized Silicon Cations. Chem. Eur. J.
2016, 22, 5376-5383. (b) Rohde, V. H. G.; Müller, M. F.; Oestreich,
M. Intramolecularly Sulfur-Stabilized Silicon Cations with Chiral
Binaphthyl Backbones: Synthesis of Three Different Motifs and
their Application in Enantioselective Diels−Alder Reactions.
Organometallics 2015, 34, 3358-3373. (c) Shaykhutdinova, P.;
Kemper, S.; Oestreich, M. Refinement of the Catalyst Backbone of
Chiral Intramolecular Silicon–Sulfur Lewis Pairs: Improved
Enantioselectivity in the Diels–Alder Reaction of Cyclohexa-1,3-
diene and Chalcone Derivatives. Eur. J. Org. Chem. 2018, 2896-
2901. (d) Pommerening, P.; Mohr, J.; Friebel, J.; Oestreich, M.
Synthesis of a Chiral Borate Counteranion, Its Trityl Salt, and
Application Thereof in Lewis-Acid Catalysis. Eur. J. Org. Chem.
2017, 2312-2316. (e) Shaykhutdinova, P.; Oestreich, M. Further
Structural Modification of Sulfur-Stabilized Silicon Cations with
Binaphthyl Backbones. Synthesis 2019, 51, 2221-2229.
(3) (a) Olah, G. A. Stable carbocations. CXVIII. General concept
and structure of carbocations based on differentiation of trivalent
(classical) carbenium ions from three-center bound penta- of
tetracoordinated (nonclassical) carbonium ions. Role of
carbocations in electrophilic reactions. J. Am. Chem. Soc. 1972, 94,
808-820. (b) Olah, G. A. 100 Years of Carbocations and Their
Significance in Chemistry. J. Org. Chem. 2001, 66, 5943-5957.
(4) Kim, K.-C.; Reed, C. A.; Elliott, D. W.; Mueller, L. J.; Tham, F.;
Lin, L.; Lambert, J. B. Crystallographic Evidence for a Free Silylium
Ion. Science 2002, 297, 825-827.
(5) Großekappenberg, H.; Reißmann, M.; Schmidtmann, M.;
Müller, T. Quantitative Assessment of the Lewis Acidity of Silylium
Ions. Organometallics 2015, 34, 4952-4958.
(6) (a) Hara, K.; Akiyama, R.; Sawamura, M. Strong Counteranion
Effects on the Catalytic Activity of Cationic Silicon Lewis Acids in
Mukaiyama Aldol and Diels-Alder Reactions. Org. Lett. 2005, 7,
5621-5623. (b) Schmidt, R. K.; Müther, K.; Mück-Lichtenfeld, C.;
Grimme, S.; Oestreich, M. Silylium Ion-Catalyzed Challenging
Diels−Alder Reactions: The Danger of Hidden Proton Catalysis with
Strong Lewis Acids. J. Am. Chem. Soc. 2012, 134, 4421-4428. (c)
Klare, H. F. T.; Bergander, K.; Oestreich, M. Taming the Silylium Ion
for Low-Temperature Diels–Alder Reactions. Angew. Chem. Int. Ed.
2009, 48, 9077-9079. (d) Nödling, A. R.; Müther, K.; Rohde, V. H. G.;
Hilt, G.; Oestreich, M. Ferrocene-Stabilized Silicon Cations as
Catalysts for Diels−Alder Reactions: Attempted Experimental
Quantification of Lewis Acidity and ReactIR Kinetic Analysis.
Organometallics 2014, 33, 302-308.
(11) Ducos, P.; Liautard, V.; Robert, F.; Landais, Y. Chiral Memory
in Silylium Ions. Chem. Eur. J. 2015, 21, 11573-11578.
(12) For an example of 5-membered ring stabilized silyl-
pyridinium, see: (a) Nokami, T.; Soma, R.; Yamamoto, Y.; Kamei, T.;
Itami, K.; Yoshida, J. Generation of pyridyl coordinated
organosilicon cation pool by oxidative Si-Si bond dissociation.
Beilstein J. Org. Chem. 2007, 3, No. 7. (b) Chauban, M.; Chuit, C.;
Corriu, R. J. P.; Mehdi, A.; Reyé, C. Study of silyl cations bearing an
aryldiamine pincer ligand. Organometallics 1996, 15, 4326-4333.
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